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TAO-DFT investigation of electronic properties of linear and cyclic carbon chains
Sonai Seenithurai1 &
Jeng-Da Chai1,2
Density functional theory
Nanoscale materials
Nanoscience and technology
Nanowires
Theory and computation
It has been challenging to adequately investigate the properties of nanosystems with radical nature using conventional electronic structure methods. We address this challenge by calculating the electronic properties of linear carbon chains (l-CC[n]) and cyclic carbon chains (c-CC[n]) with n = 10–100 carbon atoms, using thermally-assisted-occupation density functional theory (TAO-DFT). For all the cases investigated, l-CC[n]/c-CC[n] are ground-state singlets, and c-CC[n] are energetically more stable than l-CC[n]. The electronic properties of l-CC[n]/c-CC[n] reveal certain oscillation patterns for smaller n, followed by monotonic changes for larger n. For the smaller carbon chains, odd-numbered l-CC[n] are more stable than the adjacent even-numbered ones; c-CC[\(4m+2\)]/c-CC[4m] are more/less stable than the adjacent odd-numbered ones, where m are positive integers. As n increases, l-CC[n]/c-CC[n] possess increasing polyradical nature in their ground states, where the active orbitals are delocalized over the entire length of l-CC[n] or the whole circumference of c-CC[n].
Carbon is the most versatile element in forming various structures. In bulk phase, graphite and diamond, which are well-known materials, have been used for centuries. In nanoforms, fullerenes and graphene have been studied in detail for decades. In general, nanostructures can be classified into three categories: zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D) nanomaterials. Carbon forms all these nanostructures with unique shapes and properties. Over the past few decades, carbon nanomaterials have been widely studied, and applied in diverse industries1,2,3.
A number of carbon nanostructures have been synthesized and applied in different fields. The 0D carbon nanomaterials include clusters, quantum dots, nanoflakes, and buckyballs3. Among them, the C\(_{60}\) fullerene molecule (containing 12 pentagons and 20 hexagons), where the carbon atoms are \(sp^{2}\)–\(sp^{3}\)-hybridized, has been a popular carbon nanomaterial1. The discovery of C\(_{60}\) has led to the flourishment of carbon nanomaterials in various ways.
Graphite is a bulk layered material, where the \(sp^{2}\)-hybridized carbon atoms in each layer are arranged in a hexagonal lattice. The 2D carbon nanomaterial, graphene, can be obtained by mechanically exfoliating a single layer of carbon atoms from graphite2. Thus, graphene, which is a perfect arrangement of hexagons made up of \(sp^{2}\)-hybridized carbon atoms in a 2D planar surface, can be the thinnest (i.e., single-atom-thick) material synthesized ever. Graphene is a zero-gap semiconductor or semimetal with massless Dirac fermions with linear dispersion at low energy. Because of the Dirac-cone feature, graphene has huge potential in electronics applications2. The discovery of graphene has also led to the discovery of other 2D materials. Besides, if a graphene sheet can be rolled up to form a seamless cylinder, one obtains a carbon nanotube (CNT), which belongs to the class of 1D nanostructures. Note that CNTs were first observed by Iijima in 19914, well before the separation and characterization of graphene. On the basis of the direction of rolling (chirality), CNTs can be classified into three groups: chiral, zigzag, and armchair CNTs, which can have rather different electronic properties.
Apart from these well studied carbon nanoallotropes, linear carbon chains (i.e., also belonging to the class of 1D nanostructures), where the carbon atoms are sp-hybridized, have recently gained much attention because of their interesting physical and chemical properties5,6,7,8,9,10,11,12,13,14,15,16,17,18. A linear carbon chain consisting of n carbon atoms (for brevity, denoted as l-CC[n] (see Fig. 1a)) is an ideal 1D carbon nanomaterial. Kroto et al. originally designed an experiment for explaining the formation mechanism of carbon chains in outer space, which led to the serendipitous discovery of C\(_{60}\)1. In attempting to synthesize l-CC[n] (i.e., the holy grail of truly 1D carbon allotropes), significant progresses have been made recently6,11,14. Owing to their high reactivity, pristine linear carbon chains have not yet been reported. However, the linear carbon chains (containing up to 100 carbon atoms) supported inside multi-walled CNTs were realized in 2003 by Zhao et al.6. In 2015, Andrade et al.11 observed the carbon chains inside CNTs under high pressures. In 2016, Shi et al.14 demonstrated the large-scale syntheses of linear carbon chains inside double-walled CNTs by using the confined space inside the tube as a nanoreactor to grow ultra-long carbon chains (containing up to 6400 carbon atoms) in large quantities14,15. Linear carbon chains can be potential candidates for nanodevices, molecular electronics, and the building blocks of novel hybrid nanomaterials (e.g., sp–\(sp^{2}\) and sp–\(sp^{3}\) hybridized materials) by integrating with other nanostructures8,9,17. On the theoretical side, a number of relevant calculations are available9. The calculations showed that the linear carbon chains inside single-walled CNTs can modify the electronic properties of pristine single-walled CNTs significantly. It has been found that the chirality of the enclosing nanotubes can affect the properties of linear carbon chains18. Besides, recent theoretical studies showed that linear carbon chains have excellent mechanical and electrical properties9,10,14.
Structures of (a) l-CC[30] and (b) c-CC[30], each consisting of 30 carbon atoms.
On the other hand, cyclic carbon chains (for brevity, denoted as c-CC[n] (see Fig. 1b)), which are the monocyclic isomers of linear carbon chains, have also attracted considerable attention in recent years19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38. Note that c-CC[n] (where the carbon atoms are also sp-hybridized) are hypothesized to be the building blocks of fullerenes in the initial stages of growth21. Interestingly, c-CC[\(4m+2\)] (where m are positive integers) have been found to possess high stability24,25. Among them, c-CC[18] has recently been synthesized26, and some of the electronic properties of c-CC[18] have been reported. There are also a few theoretical studies on the electronic properties and applications of c-CC[18] and other cyclic carbon chains22,27,28,29,30,31,32,33,34,35,36,37,38. For example, c-CC[18] has been found to possess electron-acceptor properties, and can be dubbed as the smallest all-carbon electron acceptor28.
In general, it remains extremely difficult to synthesize both l-CC[n] and c-CC[n]. Accordingly, theoretical studies are complementary, and may provide immense information on the properties of l-CC[n] and c-CC[n]. In a recent theoretical study, it has been reported that very small l-CC[n] (n = 5–10) with even n values possess diradical nature in their ground states16. Therefore, it can be anticipated that the larger l-CC[n] and c-CC[n] could also possess radical character due to the low dimensionality of l-CC[n] and c-CC[n], respectively39. Despite its success in describing some ground-state properties, Kohn-Sham density functional theory (KS-DFT)40 can yield unreliable results for systems with radical nature41, when the conventional XC density functionals are employed. Typically, multi-reference (MR) electronic structure methods, such as the complete-active-space self-consistent-field (CASSCF), complete-active-space second-order perturbation theory (CASPT2), and related methods42,43,44,45,46,47,48, are required to reliably predict the energy and related properties of systems with radical nature. Nonetheless, accurate MR electronic structure methods can be prohibitively expensive for large systems, and hence may not be practical for studying the properties of the larger l-CC[n] and c-CC[n].
Recently, thermally-assisted-occupation density functional theory (TAO-DFT)49, which is a density functional theory with fractional orbital occupation numbers, has been formulated to tackle such challenging problems (i.e., nanosystems with radical nature), wherein an entropy contribution term (i.e., a function of the fictitious temperature \(\theta \) and orbital occupation numbers) can approximately describe strong static correlation even when the simplest local density approximation (LDA) XC density functional is employed. In TAO-DFT, one can also adopt more sophisticated XC density functionals, such as semilocal50, global hybrid51, and range-separated hybrid51,52 XC density functionals. Besides, aiming to improve the accuracy of TAO-DFT for a wide range of applications, a self-consistent scheme determining the fictitious temperature \(\theta \) in TAO-DFT has been recently proposed53. Since TAO-DFT is a computationally efficient electronic structure method, a number of strongly correlated electron systems at the nanoscale have been studied using TAO-DFT in recent years16,54,55,56,57,58,59,60,61,62. Besides, TAO-DFT has been recently shown to be useful in describing the vibrational spectra of molecules with radical nature63. In addition, TAO-DFT and related methods have recently been employed to investigate the electronic properties of several nanosystems with radical nature64,65, and have also been combined with the linear-scaling divide-and-conquer approach for the study of large systems with strong static correlation effects66.
Therefore, in the present study, we carry out TAO-DFT calculations to investigate the electronic properties of l-CC[n]/c-CC[n] with n = 10–100. Specifically, we report the electronic properties, such as the singlet-triplet energy gap, singlet-quintet energy gap, vertical ionization potential, vertical electron affinity, fundamental gap, symmetrized von Neumann entropy, active orbital occupation numbers, real-space representation of active orbitals, and relative stability of l-CC[n]/c-CC[n]. For considerably large values of n, we show that both l-CC[n] and c-CC[n] are polyradicals in their ground states, playing an important role in determining their electronic properties.
Computational details
All geometry optimizations and other calculations are performed with Q-Chem 4.467, using the 6-31G(d) basis set (i.e., a valence double-zeta polarized basis set) with a numerical quadrature that consists of 75 points in the Euler-Maclaurin radial grid and 302 points in the Lebedev angular grid. We carry out calculations using TAO-LDA49, which is TAO-DFT employing the LDA XC and \(\theta \)-dependent density functionals, with the recommended fictitious temperature \(\theta \) = 7 mhartree49.
In several recent studies46,48,49,54,55, the orbital occupation numbers obtained from TAO-LDA (with \(\theta \) = 7 mhartree) have been found to be qualitatively similar to the natural orbital occupation numbers obtained from the variational two-electron reduced-density-matrix-driven CASSCF (v2RDM-CASSCF) method (i.e., an accurate MR electronic structure method), leading to a similar trend for the radical nature of several systems.
Singlet-triplet energy gap and singlet-quintet energy gap
Aiming to obtain the energetically preferred spin state (i.e., the ground state) of l-CC[n]/c-CC[n], we obtain the energies of l-CC[n]/c-CC[n] for the lowest singlet, triplet, and quintet states by optimizing the corresponding structures with spin-unrestricted TAO-LDA, and thereafter compute the singlet-triplet energy gap of l-CC[n]/c-CC[n] using
$$\begin{aligned} E_{\text {ST}} = E_{\text {T}} - E_{\text {S}}, \end{aligned}$$
and compute the singlet-quintet energy gap of l-CC[n]/c-CC[n] using
$$\begin{aligned} E_{\text {SQ}} = E_{\text {Q}} - E_{\text {S}}, \end{aligned}$$
where \(E_{\text {Q}}\), \(E_{\text {T}}\), and \(E_{\text {S}}\) are the lowest quintet, triplet, and singlet energies, respectively, of l-CC[n]/c-CC[n] (also see Section I, Figure S1, and Figure S2 in Supplementary Information (SI)). According to their definitions, the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) reported in this work are the adiabatic singlet-triplet energy gap and adiabatic singlet-quintet energy gap, respectively, of l-CC[n]/c-CC[n]. The \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values of l-CC[n]/c-CC[n] as functions of the number of carbon atoms are presented in Figs. 2 and 3, respectively (also see Tables S1 and S2 in SI).
Singlet-triplet energy gap of l-CC[n]/c-CC[n] with (a) n = 10–30 and (b) n = 30–100, calculated using spin-unrestricted TAO-LDA.
Singlet-quintet energy gap of l-CC[n]/c-CC[n] with (a) n = 10–30 and (b) n = 30–100, calculated using spin-unrestricted TAO-LDA.
Since the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values remain positive, the l-CC[n]/c-CC[n] studied are all ground-state singlets. The \(E_{\text {ST}}\) values of the smaller l-CC[n] exhibit an odd-even oscillation pattern in which the \(E_{\text {ST}}\) values of odd-numbered l-CC[n] are larger than those of the adjacent even-numbered ones. However, such oscillations decrease with increasing n, and eventually disappear for considerably large n. Accordingly, the \(E_{\text {ST}}\) values of l-CC[n] are oscillatory only for smaller values of n (up to n = 33), and become monotonically decreasing for larger n. The \(E_{\text {SQ}}\) values of l-CC[n] decrease essentially monotonically with n (i.e., except only for n = 10).
By contrast, the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values of the smaller c-CC[n] display distinct oscillation patterns in which the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values of c-CC[\(4m+2\)]/c-CC[4m] are larger/smaller than the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values, respectively, of the adjacent odd-numbered ones, where m are positive integers. Nevertheless, with the increase of molecular size, these oscillations are progressively reduced, and eventually absent for sufficiently large n. Therefore, the \(E_{\text {ST}}\) and \(E_{\text {SQ}}\) values of c-CC[n] are oscillatory only for smaller n (up to n = 94 for \(E_{\text {ST}}\) and up to n = 85 for \(E_{\text {SQ}}\)), and become monotonically decreasing for larger values of n. Note that the reasons for these oscillation patterns have been recently provided in a quantum Monte Carlo study34.
Understanding the \(E_{\text {ST}}\) values is essential for applications that involve harnessing energy through the singlet-fission phenomenon68. Consequently, the \(E_{\text {ST}}\) values of l-CC[n]/c-CC[n] reported in the present study can provide insight into the singlet-fission phenomenon. For other relevant applications, it is worth mentioning that the electronic transport properties of c-CC[18]-based molecular devices have been recently studied38.
Vertical ionization potential, vertical electron affinity, and fundamental gap
Here, we assess if l-CC[n]/c-CC[n] are promising for photovoltaic applications. For a molecule in its ground state, the vertical ionization potential (\(\text {IP}_{v}\)) is the energy required to remove an electron from the molecule without affecting the molecular geometry, the vertical electron affinity (\(\text {EA}_{v}\)) is the energy released when an electron is added to the molecule without affecting the molecular geometry, and the fundamental gap (\(E_{g}\)) is the difference between \(\text {IP}_{v}\) and \(\text {EA}_{v}\) (i.e., \(E_{g} = \text {IP}_{v} - \text {EA}_{v}\)). Accordingly, in this work, we calculate the vertical ionization potential of ground-state l-CC[n]/c-CC[n] using
$$\begin{aligned} \text {IP}_{v} = {E}_{N-1} - {E}_{N}, \end{aligned}$$
the vertical electron affinity of ground-state l-CC[n]/c-CC[n] using
$$\begin{aligned} \text {EA}_{v} = {E}_{N} - {E}_{N+1}, \end{aligned}$$
and the fundamental gap of ground-state l-CC[n]/c-CC[n] using
$$\begin{aligned} E_{g} = {E}_{N+1} + {E}_{N-1} - 2 {E}_{N}, \end{aligned}$$
where \({E}_{N}\) is the total energy of the N-electron molecule (i.e., l-CC[n]/c-CC[n]) at the ground-state (i.e., lowest singlet state) geometry, obtained with spin-unrestricted TAO-LDA. The \(\text {IP}_{v}\) (Fig. 4a), \(\text {EA}_{v}\) (Fig. 4b), and \(E_{g}\) (Fig. 4c) values of ground-state l-CC[n]/c-CC[n] are plotted as functions of n (also see Tables S3 and S4 in SI).
(a) Vertical ionization potential, (b) vertical electron affinity, (c) fundamental gap, and (d) symmetrized von Neumann entropy of ground-state l-CC[n]/c-CC[n] with n = 10–100, calculated using spin-unrestricted TAO-LDA.
As n increases, the \(\text {IP}_{v}\) value of l-CC[n] decreases monotonically, showing a very slight odd-even pattern only for very small n. The \(\text {EA}_{v}\)/\(E_{g}\) values of the smaller l-CC[n] reveal an odd-even oscillation pattern in which the \(\text {EA}_{v}\)/\(E_{g}\) values of odd-numbered l-CC[n] are smaller/larger than those of the adjacent even-numbered ones. Nevertheless, with the increase of n, these oscillations are progressively reduced, and ultimately absent for sufficiently large n. Accordingly, the \(\text {EA}_{v}\)/\(E_{g}\) values of l-CC[n] are oscillatory only for smaller n (up to n = 21 for \(\text {EA}_{v}\) and up to n = 15 for \(E_{g}\)), and become monotonically increasing/decreasing for larger values of n.
On the other hand, the \(\text {IP}_{v}\)/\(\text {EA}_{v}\)/\(E_{g}\) values of the smaller c-CC[n] display a distinct oscillation pattern in which the \(\text {IP}_{v}\)/\(\text {EA}_{v}\)/\(E_{g}\) values of c-CC[\(4m+2\)] are larger/smaller/larger than those of the adjacent odd-numbered ones, where m are positive integers. Nonetheless, such oscillations are gradually reduced, and eventually absent with the increase of molecular size. Therefore, the \(\text {IP}_{v}\)/\(\text {EA}_{v}\)/\(E_{g}\) values of c-CC[n] are oscillatory only for smaller values of n (up to n = 61 for \(\text {IP}_{v}\), up to n = 58 for \(\text {EA}_{v}\), and up to n = 46 for \(E_{g}\)), and become monotonically decreasing/increasing/decreasing for larger n.
For each n, the \(E_{g}\) value of c-CC[n] is larger than that of l-CC[n]. Besides, the \(E_{g}\) values of l-CC[n] (with n = 24–100) and c-CC[n] (with n = 31–100) are in the range of 1 to 3 eV, showing promise for their applications in nanophotonics.
Symmetrized von Neumann entropy
To assess the radical nature of ground-state (i.e., lowest singlet state) l-CC[n]/c-CC[n], we calculate the symmetrized von Neumann entropy16,50,51,54,56,57,58,59,60,61,62,69
$$\begin{aligned} S_{\text {vN}} = -\frac{1}{2} \sum _{\sigma =\uparrow ,\downarrow } \sum _{i=1}^{\infty } \bigg \lbrace f_{i,\sigma }\ \text {ln}(f_{i,\sigma }) + (1-f_{i,\sigma })\ \text {ln}(1-f_{i,\sigma }) \bigg \rbrace , \end{aligned}$$
using spin-unrestricted TAO-LDA. Here, the occupation number \(f_{i,\sigma }\) of the \(i\)th \(\sigma \)-spin orbital (i.e., up-spin orbital or down-spin orbital) obtained with spin-unrestricted TAO-LDA, which ranges from 0 to 1, is closely related to the occupation number of the \(i\)th \(\sigma \)-spin natural orbital49,50,51. For a molecule with nonradical nature, the occupation numbers of all spin-orbitals should be close to either 0 or 1, leading to insignificant contributions to the corresponding \(S_{\text {vN}}\) value. However, for a molecule with pronounced radical nature, the occupation numbers of active spin-orbitals (i.e., the spin-orbitals that have considerable fractional occupations) can be very different from 0 and 1 (e.g., between 0.1 and 0.9); hence, the corresponding \(S_{\text {vN}}\) value is expected to increase when the occupation numbers of active spin-orbitals become closer to 0.5 and/or the number of active spin-orbitals increases.
As shown in Fig. 4d, the \(S_{\text {vN}}\) values of ground-state l-CC[n] and c-CC[n] possess rather different oscillation patterns (also see Tables S3 and S4 in SI). The \(S_{\text {vN}}\) values of the smaller l-CC[n] exhibit an odd-even oscillation pattern in which the \(S_{\text {vN}}\) values of odd-numbered l-CC[n] are smaller than those of the adjacent even-numbered ones. Nonetheless, when the system size increases, such oscillations are gradually damped, and ultimately absent for considerably large n. Therefore, the \(S_{\text {vN}}\) values of l-CC[n] are oscillatory only for smaller n (up to n = 29), and become monotonically increasing for larger n. By contrast, the \(S_{\text {vN}}\) values of the smaller c-CC[n] reveal a distinct oscillation pattern in which the \(S_{\text {vN}}\) values of c-CC[\(4m+2\)]/c-CC[4m] are smaller/larger than those of the adjacent odd-numbered ones, where m are positive integers. Nevertheless, with the increase of molecular size, these oscillations are progressively reduced, and eventually absent for sufficiently large n. Accordingly, the \(S_{\text {vN}}\) values of c-CC[n] are oscillatory only for smaller n (up to n = 73), and become monotonically increasing for larger n. Since the \(S_{\text {vN}}\) value can be regarded as a quantitative measure of the radical nature of a molecule, the larger l-CC[n]/c-CC[n] are expected to exhibit increasing polyradical nature in their ground states.
Active orbital occupation numbers
To understand the reason that the symmetrized von Neumann entropy grows with the size of l-CC[n]/c-CC[n], it is instructive and informative to present the active orbital occupation numbers of ground-state l-CC[n]/c-CC[n] (consisting of N electrons), obtained with spin-restricted TAO-LDA, wherein the highest occupied molecular orbital (HOMO) is defined as the \((N/2)\)th orbital, the lowest unoccupied molecular orbital (LUMO) is defined as the \((N/2+1)\)th orbital, and so forth49,51,58,60,61,62. Here, the active orbitals are regarded as the orbitals with an occupation number ranging from 0.2 to 1.8 (i.e., the active spin-orbitals are regarded as the spin-orbitals with an occupation number ranging from 0.1 to 0.9).
As shown in Fig. 5, the active orbital occupation numbers of the smaller l-CC[n] (e.g., up to n = 20) reveal odd-even oscillation patterns, indicating that odd-numbered l-CC[n] possess nonradical nature (i.e., the occupation numbers of all orbitals are close to either 0 or 2), and even-numbered l-CC[n] possess pronounced diradical nature (i.e., the active orbitals are HOMO and LUMO). However, with the increase of the size of l-CC[n], the active orbital occupation numbers become closer to 1 and/or the number of active orbitals increases, suggesting an increasing polyradical nature of the larger l-CC[n].
Active orbital occupation numbers (HOMO−5,...,HOMO−1, HOMO, LUMO, LUMO+1,...,and LUMO+5) of ground-state l-CC[n] with (a) n = 10–30 and (b) n = 30–100, calculated using spin-restricted TAO-LDA. For brevity, HOMO/LUMO is denoted as H/L.
In contrast to l-CC[n], the active orbital occupation numbers of c-CC[n] display very different patterns (see Fig. 6). In particular, the smaller c-CC[\(4m+2\)] (e.g., up to \(4m+2\) = 46) possess nonradical nature (i.e., the occupation numbers of all orbitals are close to either 0 or 2), and hence are relatively more stable than c-CC[4m], c-CC[\(4m+1\)], and c-CC[\(4m+3\)], where m are positive integers. By contrast, c-CC[4m] (where m are positive integers) possess tetraradical nature (i.e., the active orbitals are HOMO−1, HOMO, LUMO, and LUMO+1). Nevertheless, with the increase of the size of c-CC[n], the active orbital occupation numbers become closer to 1 and/or the number of active orbitals increases, suggesting an increasing polyradical nature of the larger c-CC[n].
Active orbital occupation numbers (HOMO−5,...,HOMO−1, HOMO, LUMO, LUMO+1,...,and LUMO+5) of ground-state c-CC[n] with (a) n = 10–30 and (b) n = 30–100, calculated using spin-restricted TAO-LDA. For brevity, HOMO/LUMO is denoted as H/L.
On the basis of the active orbital occupation numbers, the smaller odd-numbered l-CC[n] and the smaller c-CC[\(4m+2\)] (where m are positive integers) possess nonradical nature in their ground states, being consistent with the analyses of the other electronic properties (e.g., the larger \(E_{\text {ST}}\) values, larger \(E_{\text {SQ}}\) values, larger \(E_{g}\) values, and smaller \(S_{\text {vN}}\) values) of these relatively stable linear carbon chains and cyclic carbon chains, respectively. Accordingly, this study confirms the high stability of the smaller c-CC[\(4m+2\)]24,25, including the recently synthesized c-CC[18]26. On the other hand, c-CC[4m] (where m are positive integers) possess tetraradical nature in their ground states, also showing consistency with the analyses of the other electronic properties (e.g., the smaller \(E_{\text {ST}}\) values, smaller \(E_{\text {SQ}}\) values, smaller \(E_{g}\) values, and larger \(S_{\text {vN}}\) values) of these relatively unstable cyclic carbon chains.
Real-space representation of active orbitals
Here, we plot the real-space representation of the active orbitals, such as HOMO−2, HOMO−1, HOMO, LUMO, LUMO+1, and LUMO+2, for the ground states of some representative l-CC[n] (see Figs. 7 and 8) and c-CC[n] (see Figs. 9 and 10), obtained with spin-restricted TAO-LDA (also see Figures S1 to S6 in SI for more illustrative cases). The real-space representation analysis indicates that the active orbitals are delocalized over the entire length of l-CC[n] or the whole circumference of c-CC[n]. As the electrical conductivities of molecules consisting of many delocalized electrons are likely to be high70, it can be anticipated that l-CC[n]/c-CC[n] should be highly conductive due to the presence of delocalized electrons.
Real-space representation of HOMO−2 (1.952), HOMO−1 (1.951), HOMO (1.049), LUMO (1.049), LUMO+1 (0.000), and LUMO+2 (0.000) of ground-state l-CC[10], calculated using spin-restricted TAO-LDA, at isovalue = 0.02 e/Å\(^3\). The orbital occupation numbers are given in parentheses. For brevity, HOMO/LUMO is denoted as H/L.
Real-space representation of HOMO−2 (2.000), HOMO−1 (2.000), HOMO (2.000), LUMO (0.000), LUMO+1 (0.000), and LUMO+2 (0.000) of ground-state c-CC[10], calculated using spin-restricted TAO-LDA, at isovalue = 0.02 e/Å\(^3\). The orbital occupation numbers are given in parentheses. For brevity, HOMO/LUMO is denoted as H/L.
Relative stability
We carry out spin-unrestricted TAO-LDA calculations to investigate the relative stability of l-CC[n] and c-CC[n] (i.e., the two isomers) in their ground states, which is examined by
$$\begin{aligned} E_{rel} = E_{\text {S}}({\textit{l-}CC}) - E_{\text {S}}({\textit{c-}CC}). \end{aligned}$$
Here, \(E_{rel}\) is the relative energy of ground-state l-CC[n] with respect to ground-state c-CC[n], and \(E_{\text {S}}({\textit{l-}CC})\) and \(E_{\text {S}}({\textit{c-}CC})\) are the lowest singlet state (i.e., ground state) energies of l-CC[n] and c-CC[n], respectively.
The \(E_{rel}\) value as a function of the number of carbon atoms is plotted in Fig. 11 (also see Table S5 in SI). As the system size increases, the \(E_{rel}\) values are oscillatory only for smaller values of n (up to n = 59), and become monotonically increasing for larger n. For all the cases investigated, c-CC[n] are energetically more stable than l-CC[n], showing the significance of cyclic topology.
Relative energy of ground-state l-CC[n] with respect to ground-state c-CC[n] for n = 10–100, calculated using spin-unrestricted TAO-LDA.
In conclusion, we have employed TAO-DFT to investigate the electronic properties (e.g., the singlet-triplet energy gap, singlet-quintet energy gap, vertical ionization potential, vertical electron affinity, fundamental gap, symmetrized von Neumann entropy, active orbital occupation numbers, real-space representation of active orbitals, and relative stability) of l-CC[n]/c-CC[n] with n = 10–100 carbon atoms. For considerably large n, l-CC[n]/c-CC[n] are polyradicals in their ground states, playing an important role in determining their electronic properties. In view of their polyradical nature, it can be unreliable to study the properties of the larger l-CC[n]/c-CC[n] using KS-DFT with the traditional XC energy functionals, and it can be computationally intractable to study the properties of the larger l-CC[n]/c-CC[n] using accurate MR electronic structure methods. Consequently, it is well justified to study the electronic properties of l-CC[n]/c-CC[n] using TAO-DFT (i.e., a computationally efficient electronic structure method for nanosystems with radical nature) in this work.
For all the cases investigated, l-CC[n] and c-CC[n] are ground-state singlets, and c-CC[n] are energetically more stable than l-CC[n]. The electronic properties of l-CC[n] and c-CC[n] display peculiar oscillation patterns for smaller values of n, followed by monotonic changes for larger values of n. For the smaller carbon chains, odd-numbered l-CC[n] are more stable than the adjacent even-numbered ones, and c-CC[\(4m+2\)]/c-CC[4m] (where m are positive integers) are more/less stable than the adjacent odd-numbered ones. With the increase of n, l-CC[n] and c-CC[n] possess increasing polyradical nature in their ground states, with the active orbitals being delocalized over the entire length of l-CC[n] or the whole circumference of c-CC[n].
On the basis of our TAO-LDA results, the smaller c-CC[\(4m+2\)] (up to \(4m+2\) = 22, where m are positive integers) possess nonradical nature and sizable singlet-triplet energy gaps (e.g., larger than 20 kcal/mol). In view of their high stability, it can be anticipated that these relatively stable cyclic carbon chains, such as c-CC[10], c-CC[14], c-CC[18], and c-CC[22], are likely to be synthesized in the near future. Note that among them, c-CC[18] have been recently synthesized26.
While the method adopted (i.e., TAO-LDA with the fictitious temperature \(\theta \) = 7 mhartree49) is computationally efficient for the study of nanosystems with radical nature, a few limitations remain. First, owing to the use of LDA XC and \(\theta \)-dependent density functionals in TAO-DFT, TAO-LDA can yield the self-interaction error41,49, 51, and hence bond length alternation (BLA) can be suppressed30. Second, the present \(\theta \) value is system-independent, and hence the static correlation associated with electronic systems can only be described approximately53. Note that the first issue can be greatly resolved by using the long-range corrected hybrid XC functionals71,72 in TAO-DFT51,52 for an improved description of nonlocal exchange effects, and the second issue can be greatly resolved by using the respective self-consistent scheme for determining the \(\theta \) value53. Accordingly, we plan to work in this direction in the future.
On the other hand, to fully understand the impact of molecular geometries (e.g., BLA) on the electronic properties (e.g., the singlet-triplet energy gap, singlet-quintet energy gap, fundamental gap, and active orbital occupation numbers) of l-CC[n]/c-CC[n], it is essential to employ accurate multi-reference methods, such as the CASSCF (for static correlation) and possibly, CASPT2 (for both static correlation and dynamical correlation) methods, for geometry optimizations and single-point energy calculations on different spin states (e.g., the lowest singlet, triplet, and quintet states) of l-CC[n]/c-CC[n]. As this task can be computationally intractable, the electronic properties of l-CC[n]/c-CC[n] calculated using reasonably accurate and relatively inexpensive multi-reference methods are needed.
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Kroto, H. W., Heath, J. R., O'Brien, S. C., Curl, R. F. & Smalley, R. E. C\(_{60}\): Buckminsterfullerene. Nature 318, 162–163 (1985).
ADS CAS Google Scholar
Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).
ADS CAS PubMed Google Scholar
Georgakilas, V., Perman, J. A., Tucek, J. & Zboril, R. Broad family of carbon nanoallotropes: Classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures. Chem. Rev. 115, 4744–4822 (2015).
Iijima, S. Helical microtubules of graphitic carbon. Nature 354, 56–58 (1991).
Baeyer, A. Ueber polyacetylenverbindungen. Ber. Dtsch. Chem. Ges. 18, 2269–2281 (1885).
Zhao, X., Ando, Y., Liu, Y., Jinno, M. & Suzuki, T. Carbon nanowire made of a long linear carbon chain inserted inside a multiwalled carbon nanotube. Phys. Rev. Lett. 90, 187401 (2003).
ADS PubMed Google Scholar
Belau, L. et al. Ionization thresholds of small carbon clusters: Tunable VUV experiments and theory. J. Am. Chem. Soc. 129, 10229–10243 (2007).
Jin, C., Lan, H., Peng, L., Suenaga, K. & Iijima, S. Deriving carbon atomic chains from graphene. Phys. Rev. Lett. 102, 205501 (2009).
Liu, M., Artyukhov, V. I., Lee, H., Xu, F. & Yakobson, B. I. Carbyne from first principles: Chain of C atoms, a nanorod or a nanorope. ACS Nano 7, 10075–10082 (2013).
Artyukhov, V. I., Liu, M. & Yakobson, B. I. Mechanically induced metal-insulator transition in carbyne. Nano Lett. 14, 4224–4229 (2014).
Andrade, N. F. et al. Linear carbon chains under high-pressure conditions. J. Phys. Chem. C 119, 10669–10676 (2015).
Banhart, F. Chains of carbon atoms: A vision or a new nanomaterial?. Beilstein J. Nanotechnol. 6, 559–569 (2015).
Casari, C. S., Tommasini, M., Tykwinski, R. R. & Milani, A. Carbon-atom wires: 1-D systems with tunable properties. Nanoscale 8, 4414–4435 (2016).
Shi, L. et al. Confined linear carbon chains as a route to bulk carbyne. Nat. Mater. 15, 634–639 (2016).
Shi, L. et al. Electronic band gaps of confined linear carbon chains ranging from polyyne to carbyne. Phys. Rev. Mater. 1, 075601 (2017).
Seenithurai, S. & Chai, J.-D. Effect of Li termination on the electronic and hydrogen storage properties of linear carbon chains: A TAO-DFT study. Sci. Rep. 7, 4966 (2017).
ADS PubMed PubMed Central Google Scholar
Casari, C. S. & Milani, A. Carbyne: From the elusive allotrope to stable carbon atom wires. MRS Commun. 8, 207–219 (2018).
Heeg, S., Shi, L., Poulikakos, L. V., Pichler, T. & Novotny, L. Carbon nanotube chirality determines properties of encapsulated linear carbon chain. Nano Lett. 18, 5426–5431 (2018).
Hoffmann, R. Extended Hückel theory-V: Cumulenes, polyenes, polyacetylenes and C\(_{n}\). Tetrahedron 22, 521–538 (1966).
Yang, S. et al. UPS of 2–30-atom carbon clusters: Chains and rings. Chem. Phys. Lett. 144, 431–436 (1988).
von Helden, G., Gotts, N. G. & Bowers, M. T. Experimental evidence for the formation of fullerenes by collisional heating of carbon rings in the gas phase. Nature 363, 60–63 (1993).
Handschuh, H., Ganteför, G., Kessler, B., Bechthold, P. S. & Eberhardt, W. Stable configurations of carbon clusters: Chains, rings, and fullerenes. Phys. Rev. Lett. 74, 1095–1098 (1995).
Kaizu, K. et al. Neutral carbon cluster distribution upon laser vaporization. J. Chem. Phys. 106, 9954 (1997).
Van Orden, A. & Saykally, R. J. Small carbon clusters: Spectroscopy, structure, and energetics. Chem. Rev. 98, 2313–2358 (1998).
Wakabayashi, T., Momose, T. & Shida, T. Mass spectroscopic studies of laser ablated carbon clusters as studied by photoionization with 10.5 eV photons under high vacuum. J. Chem. Phys. 111, 6260–6263 (1999).
Kaiser, K. et al. An \(sp\)-hybridized molecular carbon allotrope, cyclo[18]carbon. Science 365, 1299–1301 (2019).
Lu, T., Chen, Q. & Liu, Z. A thorough theoretical exploration of intriguing characteristics of cyclo[18]carbon: Geometry, bonding nature, aromaticity, weak interaction, reactivity, excited states, vibrations, molecular dynamics and various molecular properties. ChemRxiv, Preprint. https://doi.org/10.26434/chemrxiv.11320130.v2 (2019).
Stasyuk, A. J., Stasyuk, O. A., Solà, M. & Voityuk, A. A. Cyclo[18]carbon: The smallest all-carbon electron acceptor. Chem. Commun. 56, 352–355 (2020).
Martin, J. M. L., El-Yazal, J. & François, J.-P. Structure and vibrational spectra of carbon clusters C\(_{n}\) (\(n\) = 2–10, 12, 14, 16, 18) using density functional theory including exact exchange contributions. Chem. Phys. Lett. 242, 570–579 (1995).
Heaton-Burgess, T. & Yang, W. Structural manifestation of the delocalization error of density functional approximations: C\(_{4N+2}\) rings and C\(_{20}\) bowl, cage, and ring isomers. J. Chem. Phys. 132, 234113 (2010).
Shi, B., Yuan, L., Tang, T., Yuan, Y. & Tang, Y. Study on electronic structure and excitation characteristics of cyclo[18]carbon. Chem. Phys. Lett. 741, 136975 (2020).
Pereira, Z. S. & da Silva, E. Z. Spontaneous symmetry breaking in cyclo[18]carbon. J. Phys. Chem. A 124, 1152–1157 (2020).
Li, M. et al. Potential molecular semiconductor devices: Cyclo-C\(_{n}\) (\(n\) = 10 and 14) with higher stabilities and aromaticities than acknowledged cyclo-C\(_{18}\). Phys. Chem. Chem. Phys. 22, 4823–4831 (2020).
Hong, I. et al. Competition between Hückel's rule and Jahn-Teller distortion in small carbon rings: A quantum Monte Carlo study. J. Phys. Chem. A 124, 3636–3640 (2020).
Brémond, É, Pérez-Jiménez, ÁJ., Adamo, C. & Sancho-García, J. C. sp-hybridized carbon allotrope molecular structures: An ongoing challenge for density-functional approximations. J. Chem. Phys. 151, 211104 (2019).
Zou, W., Tao, Y. & Kraka, E. Systematic description of molecular deformations with Cremer-Pople puckering and deformation coordinates utilizing analytic derivatives: Applied to cycloheptane, cyclooctane, and cyclo[18]carbon. J. Chem. Phys. 152, 154107 (2020).
Baryshnikov, G. V., Valiev, R. R., Kuklin, A. V., Sundholm, D. & Ågren, H. Cyclo[18]carbon: Insight into electronic structure, aromaticity, and surface coupling. J. Phys. Chem. Lett. 10, 6701–6705 (2019).
Zhang, L., Li, H., Feng, Y. P. & Shen, L. Diverse transport behaviors in cyclo[18]carbon-based molecular devices. J. Phys. Chem. Lett. 11, 2611–2617 (2020).
Brus, L. Size, dimensionality, and strong electron correlation in nanoscience. Acc. Chem. Res. 47, 2951–2959 (2014).
Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).
ADS MathSciNet Google Scholar
Cohen, A. J., Mori-Sánchez, P. & Yang, W. Challenges for density functional theory. Chem. Rev. 112, 289–320 (2012).
Andersson, K., Malmqvist, P. -Å & Roos, B. O. Second-order perturbation theory with a complete active space self-consistent field reference function. J. Chem. Phys. 96, 1218–1226 (1992).
Hachmann, J., Dorando, J. J., Aviles, M. & Chan, G. K. L. The radical character of the acenes: A density matrix renormalization group study. J. Chem. Phys. 127, 134309 (2007).
Gidofalvi, G. & Mazziotti, D. A. Active-space two-electron reduced-density-matrix method: Complete active-space calculations without diagonalization of the \(N\)-electron hamiltonian. J. Chem. Phys. 129, 134108 (2008).
Gryn'ova, G., Coote, M. L. & Corminboeuf, C. Theory and practice of uncommon molecular electronic configurations. WIREs Comput. Mol. Sci. 5, 440–459 (2015).
Fosso-Tande, J., Nguyen, T.-S., Gidofalvi, G. & DePrince, A. E. III. Large-scale variational two-electron reduced-density-matrix-driven complete active space self-consistent field methods. J. Chem. Theory Comput. 12, 2260–2271 (2016).
Battaglia, S., Faginas-Lago, N., Andrae, D., Evangelisti, S. & Leininger, T. Increasing radical character of large [\(n\)]cyclacenes unveiled by wave function theory. J. Phys. Chem. A 121, 3746–3756 (2017).
Mullinax, J. W. et al. Heterogeneous CPU + GPU algorithm for variational two-electron reduced-density matrix-driven complete active-space self-consistent field theory. J. Chem. Theory Comput. 15, 6164–6178 (2019).
Chai, J.-D. Density functional theory with fractional orbital occupations. J. Chem. Phys. 136, 154104 (2012).
Chai, J.-D. Thermally-assisted-occupation density functional theory with generalized-gradient approximations. J. Chem. Phys. 140, 18A521 (2014).
Chai, J.-D. Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes. J. Chem. Phys. 146, 044102 (2017).
Xuan, F., Chai, J.-D. & Su, H. Local density approximation for the short-range exchange free energy functional. ACS Omega 4, 7675–7683 (2019).
Lin, C.-Y., Hui, K., Chung, J.-H. & Chai, J.-D. Self-consistent determination of the fictitious temperature in thermally-assisted-occupation density functional theory. RSC Adv. 7, 50496–50507 (2017).
Wu, C.-S. & Chai, J.-D. Electronic properties of zigzag graphene nanoribbons studied by TAO-DFT. J. Chem. Theory Comput. 11, 2003–2011 (2015).
Yeh, C.-N. & Chai, J.-D. Role of Kekulé and non-Kekulé structures in the radical character of alternant polycyclic aromatic hydrocarbons: A TAO-DFT study. Sci. Rep. 6, 30562 (2016).
ADS CAS PubMed PubMed Central Google Scholar
Seenithurai, S. & Chai, J.-D. Effect of Li adsorption on the electronic and hydrogen storage properties of acenes: A dispersion-corrected TAO-DFT study. Sci. Rep. 6, 33081 (2016).
Wu, C.-S., Lee, P.-Y. & Chai, J.-D. Electronic properties of cyclacenes from TAO-DFT. Sci. Rep. 6, 37249 (2016).
Yeh, C.-N., Wu, C., Su, H. & Chai, J.-D. Electronic properties of the coronene series from thermally-assisted-occupation density functional theory. RSC Adv. 8, 34350–34358 (2018).
Seenithurai, S. & Chai, J.-D. Electronic and hydrogen storage properties of Li-terminated linear boron chains studied by TAO-DFT. Sci. Rep. 8, 13538 (2018).
Chung, J.-H. & Chai, J.-D. Electronic properties of Möbius cyclacenes studied by thermally-assisted-occupation density functional theory. Sci. Rep. 9, 2907 (2019).
Seenithurai, S. & Chai, J.-D. Electronic properties of linear and cyclic boron nanoribbons from thermally-assisted-occupation density functional theory. Sci. Rep. 9, 12139 (2019).
Deng, Q. & Chai, J.-D. Electronic properties of triangle-shaped graphene nanoflakes from TAO-DFT. ACS Omega 4, 14202–14210 (2019).
Hanson-Heine, M. W. D. Static correlation in vibrational frequencies studied using thermally-assisted-occupation density functional theory. Chem. Phys. Lett. 739, 137012 (2020).
Pérez-Guardiola, A. et al. The role of topology in organic molecules: Origin and comparison of the radical character in linear and cyclic oligoacenes and related oligomers. Phys. Chem. Chem. Phys. 20, 7112–7124 (2018).
Pérez-Guardiola, A. et al. From cyclic nanorings to single-walled carbon nanotubes: Disclosing the evolution of their electronic structure with the help of theoretical methods. Phys. Chem. Chem. Phys. 21, 2547–2557 (2019).
Yoshikawa, T., Doi, T. & Nakai, H. Finite-temperature-based linear-scaling divide-and-conquer self-consistent field method for static electron correlation systems. Chem. Phys. Lett. 725, 18–23 (2019).
Shao, Y. et al. Advances in molecular quantum chemistry contained in the Q-Chem 4 program package. Mol. Phys. 113, 184–215 (2015).
Smith, M. B. & Michl, J. Singlet fission. Chem. Rev. 110, 6891–6936 (2010).
Rivero, P., Jiménez-Hoyos, C. A. & Scuseria, G. E. Entanglement and polyradical character of polycyclic aromatic hydrocarbons predicted by projected Hartree-Fock theory. J. Phys. Chem. B 117, 12750–12758 (2013).
Che, Y. et al. Enhancing one-dimensional charge transport through intermolecular \(\pi \)-electron delocalization: Conductivity improvement for organic nanobelts. J. Am. Chem. Soc. 129, 6354–6355 (2007).
Cohen, A. J., Mori-Sánchez, P. & Yang, W. Development of exchange-correlation functionals with minimal many-electron self-interaction error. J. Chem. Phys. 126, 191109 (2007).
Lin, Y.-S., Li, G.-D., Mao, S.-P. & Chai, J.-D. Long-range corrected hybrid density functionals with improved dispersion corrections. J. Chem. Theory Comput. 9, 263–272 (2013).
This work was supported by the Ministry of Science and Technology of Taiwan (Grant No. MOST107-2628-M-002-005-MY3), National Taiwan University (Grant No. NTU-CDP-105R7818), and the National Center for Theoretical Sciences of Taiwan.
Department of Physics, National Taiwan University, Taipei, 10617, Taiwan
Sonai Seenithurai & Jeng-Da Chai
Center for Theoretical Physics and Center for Quantum Science and Engineering, National Taiwan University, Taipei, 10617, Taiwan
Jeng-Da Chai
Sonai Seenithurai
S.S. and J.-D.C. designed the project, performed the data analysis, and wrote the manuscript. S.S. carried out the calculations.
Correspondence to Jeng-Da Chai.
Supplementary Information 1.
Seenithurai, S., Chai, JD. TAO-DFT investigation of electronic properties of linear and cyclic carbon chains. Sci Rep 10, 13133 (2020). https://doi.org/10.1038/s41598-020-70023-z
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Rustic Willow reopens in Meshoppen
Brooke Williams / Published: September 11, 2019
STAFF PHOTO/BROOKE WILLIAMS Cassie Holley often receives help at Rustic Willow in Meshoppen from her son Kallam Kiper.
Cassie Holley has always seen value in transforming old pieces of decor into new treasures.
"I grew up going to yard sales, flea markets and auctions with my grandfather," Holley said. "My mother passed away when I was 8, but I remember growing up, we would go to thrift stores. She would bring something home and reuse it or repurpose it or paint it to make it match our home, so it's been something that I've always had in my blood."
Back in 2014, Holley turned her hobby into a business by opening Rustic Willow, a home decor shop on Bunnell Road in Meshoppen.
A few major life changes for Holley led to the shop's closing in 2016, though she kept Rustic Willow going on the side while also offering her services to a different local business.
In July, she was finally able to reopen her shop in its original location.
Through Rustic Willow, Holley offers furniture refinishing services for clients with pick up and drop off options.
"I have also been asked to do so much as people's kitchen cabinets. I will refinish any surface," se said. "I also do custom signs, and then I have been running 'claim it and paint it' on my Facebook page."
With 'claim it and paint it,' Holley posts photos of pieces that are in good condition, but not always aesthetically pleasing.
Customers could either buy the piece as is or ask Holley to give it a face lift.
"A single color and distress and a seal, or I can even do more than one color or I can restain it," she explained. "I can basically do anything that the client wants."
Rustic Willow also carries merchandise for sale, including signs and other home decorations.
"I've spent the last couple weeks coming up with new designs," she said. "About 90-95 percent of the stuff in here is handmade, handpainted, done by me."
Right now, customers can expect seasonal autumn and Halloween merchandise with some winter and Christmas items in addition to everyday decor.
This October, Holley also plans to double the shop's square footage.
"We're getting another building and doubling our parking as well," she said. "I opened back here at this location the first weekend of July and it has just expanded so quickly."
"We might be out in the middle of nowhere, but people don't mind coming out here," she added.
With her handmade goods, Holley tries to think as unique as possible.
"Everybody loves the humor signs, the ones that put a good smile on someone's face, so I try to do those style signs," she said. "I try not to carry anything that anyone else local has. I try to keep my pieces and my items a little bit different."
Along with the shop's expansion, Holley also hopes to enhance Rustic Willow's online presence.
Having recently been approved for an account with Amazon Homemade, she could find new clientele all around the country.
In the future, she also may consider breaking into jewelry and apparel, as well as wine and coffee tumblers.
Rustic Willow on 23 Bunnell Road opens for the public from 10 a.m. to 4 p.m. on Fridays and Saturdays, with all other days by appointment.
In May, Holley also began selling her products inside Central Station Marketplace and Antiques on Keyser Avenue in Scranton, and two weeks ago at Your Needful Things in Binghamton.
When Rustic Willow isn't open, Holley can either be found shopping for supplies, picking up to-be-completed furniture, delivering completed pieces to clients or brainstorming new ideas.
However, the mother of five tries to reserve Sundays for family time.
"There's so much to keep the wheels going," she said. "Every day, it's usually sunup to sundown."
While being a full-time business owner and parent could get hectic, Holley wouldn't have it any other way since she was able to make her hobby a career.
"It's like therapy for me," she said. "It's something I really enjoy doing."
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How to watch Korea's popular drama "Extraordinary You" outside Korea?
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How to watch the sixth season of the Korean variety show "See Your Voice" overseas?
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How to watch the paternity test program outside the United States: "Maury show"?
There is a high-end view of a US variety show on YouTube. That's right, it's the 28-year-old "old age" paternity test program - "The Maury Povich Show". The slogan of the show is: If you can't find your child's father, come to MAURY SHOW. The program group is free to do parent-child identification for the guests, and the number of applicants for the program is endless. The host and the audience are purely eating people, and watching the lively is not too big. This is such a "Green Hat Identification Department" program, which is as hot as overseas in all the variety shows. Because it is a variety show in the United States, it is not available to the US Overseas Party to use FlyVPN to connect to US nodes for viewing.
Mauri Show (Maury show) was first launched by Paramount's domestic TV and Mopo production company. It has been on the market since September 9, 1991. It has been a ace show for a total of 28 years. Unlike the domestic variety show such as "Extreme Challenge", "Morley Show" is more inclined to lead the audience to watch the lively poisonous chicken soup program. The guests are ordinary amateurs. The common feature is that they don't know who the relatives of the baby are! ?
Summarize the reasons for the above phenomenon, or too many people who have slept, do not know which is the child of his relatives! Either there is a gunman who brought the baby to the door, but it is obviously not a relative!
When the host finally announced who his relatives were, he could always make one of the men and women dance. This program is so hot... It is also inseparable from the large-scale dance scene. Together with the people who eat melons all over the world, there is such a thing to tear up and fly together, the green hat celebrates one color, specializing in How can you not watch the lively programs? Don't mention 28 years, the ratings will not be low for a long time.
Due to the moment when the identification results came out, the guests' reaction was too fierce. Netizens who are not familiar with the US welfare system may be confused about this phenomenon. analyzes it.
In the United States, whether the child is an adult or a newborn baby, the biological father has to pay a maintenance fee, and the child's mother can get the living expenses during the "reasonable no work" as long as she has not married again. Moreover, this support is directly linked to personal income, and the more you earn, the more you give.
Therefore, this is why the guests always have a dance and dance when they know the results of the appraisal. Even in the B station, youtube and other platforms have a dedicated collection of Mo Li Xiu dance. This program is a source of happiness for netizens. Due to the regional copyright restrictions, you can't see the users of this program. You can use FlyVPN to unlock the US website with one click and easily pursue the drama. And users who sign up for FlyVPN for the first time enjoy 14 days of free access and can access many free nodes around the world.
Labels: American TV show, USA VPN, 绕过区域块, 绕过地域限制
How to get the IP address of Ho Chi Minh City outside Vietnam?
Ho Chi Minh City also known by its former name of Saigon is the most populous city in Vietnam. It is the economic, trade, transportation and cultural center of Vietnam. As an important city in Asia, Ho Chi Minh City attracts a large number of immigrants and tourists. Japanese, Koreans, Chinese and a large number of European and American tourists come to visit the city. A VPN with a Vietnam server is a must-have software for all cross-border visitors. FlyVPN is recommended.
Ho Chi Minh City is a very complex city filled with cultures from different countries. Although Ho Chi Minh City is an Asian country, its cuisine, architecture, coffee is French-style because it used to be a French colony. It is also known as the Paris of the East. Therefore, in addition to tourists from Asia, tourists from Europe and the United States often travel to Vietnam too. Cross border travel usually has Internet restrictions. If you are outside of Vietnam, you will need a VPN to access the Vietnam website.
In a population of about 96 million, 64 million Vietnamese are online, which adds up to a remarkable Internet penetration rate of 67%. Vietnam ranks seventh in the world in terms of Facebook users. But a Vietnam IP address cannot access websites such as the BBC. Use FlyVPN, you can get an IP address of the corresponding region to unlock the website.
FlyVPN is an enterprise-class global VPN software with stable servers on five continents. Connect to the world with one click. You can easily get a Ho Chi Minh City address and connect to other countries' networks. You can avoid the data monitoring of major websites and enjoy a complete, unfettered network experience without any restrictions and annoying ads.
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Google searches for FlyVPN and opens the website
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Select a Ho Chi Minh City server, click connect option. Visit the Ho Chi Minh City website easily
Ho Chi Minh City VPN, why choose FlyVPN?
Enjoy the Internet with no restrictions. FlyVPN offers access to more than 30 of the most popular countries. No matter where you are, you can easily enjoy the Internet with no restrictions and anonymous access to the entire Internet.
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Unlimited network data transmission. FlyVPN servers have no bandwidth or traffic restrictions. While browsing the web, watching videos and playing games, it brings you the ultimate Internet experience.
What servers does FlyVPN have?
FlyVPN currently has servers in 34 countries around the world, and servers in other countries are also expanding. With 256-AES bit technology, users can use this VPN to protect their own network security and avoid information leakage. In addition, FlyVPN has a reasonable price, users can get 14 days free VPN when register on a mobile phone for the first time, and there are numerous free servers, it is worthy of user choice.
More servers, click on the link to enter the official website to view:https://www.flyvpn.com/en/freetrial
Labels: change ip, iOS VPN, iPhone VPN, Vietnam VPN,, 绕过区域封锁
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text:
Tesla China Sales Topped 70,000 In December
Moto2 World Championship Race Results From Qatar II (Updated) – Roadracing World Magazine
Editorial Note: Use the scroll and zoom tools in the bottom left corner of the PDF viewers to better see all of the results.
Moto2 Race Results
Moto2 Point Standings
More, from a press release issued by Dorna:
To the wire: Lowes fends off Gardner in a tense Moto2™ take two
The Brit and the Aussie were at it again, but this time it went to the wire – and it's Raul Fernandez who completed the podium
Sam Lowes (Elf Marc VDS Racing Team) leaves Losail with a clean sweep after his second victory in as many weekends, the Brit impressing once again to become the first British rider to win the opening two races of an intermediate class campaign since Mike Hailwood did it in 1966. Quite a stat, but the sailing wasn't perfectly smooth as Remy Gardner (Red Bull KTM Ajo) was his key challenger once again, this time around even closer than the first. The Aussie pushed the number 22 to the wire, and just lost out by two tenths after hanging back from being too optimistic at the final corner despite temptation. In third, rookie sensation Raul Fernandez (Red Bull KTM Ajo) turned his increasing experience into his first Moto2™ podium after another impressive ride.
Marco Bezzecchi (Sky Racing Team VR46) took the holeshot after some shuffling off the line, with Lowes in second and Gardner third. Raul Fernandez was a little wide and had to settle for fourth, but the quartet in the lead immediately started to haul Kalex and make a gap back to the chasing pack led by Aron Canet (Solunion Aspar Team).
Heading onto Lap 4, the lead changed. Lowes tucked in behind Bezzecchi on the straight and made a Turn 1 move stick, and the Brit put the pedal to the metal to move half a second clear. But Gardner, seeing Lowes getting into his groove, started making moves too and just about scraped past Fernandez after losing out to his teammate.
Bezzecchi soon went from P2 to P4 as both Red Bull KTM Ajos drafted the Italian and set their sights on Lowes, who wasn't pulling any further clear. Soon enough, Gardner was hounding the Brit, and Raul Fernandez and Bezzecchi were just waiting in the wings…
By Lap 13, Lowes was asking questions of Gardner, although Raul Fernandez was still sticking with the two elder Moto2™ statesmen. Bezzecchi was losing touch though, the Italian 1.5 seconds back from Raul Fernandez. With six to go, it looked like it was Lowes vs Red Bull KTM Ajo for victory under the lights.
The fastest lap of the race, a 1:59.131, was then set by Gardner as the race entered the final five laps. 0.7s split the trio, of which only 0.2s sat between Lowes and Gardner. The Qatar race winner looked to have the edge in the opening half of the lap, the Qatar GP runner-up looked quicker in the latter. But there was still no change though with three laps to go as a trio of 1:59.1s for Gardner still wasn't enough. Raul Fernandez was clinging on, but the Spaniard was 0.7s away from his teammate's tailpipes as the leaders swept over the line.
Lowes responded to Gardner's pressure, but the Australian always seemed to find an answer in return. Heading into the latter half of the last lap, it was now or never and Gardner was right up behind Lowes. Coming out of Turn 14, they were closer than ever. The number 87 looked tempted as he looked down the inside, but no move came there or just after and it was down to the final corner and drag to the line. Lowes braked late into Turn 16, Gardner tried to get on the gas early but the number 22 got the power down. The Brit took the chequered flag 0.190s ahead after a classic game of chess, and both riders set their best laps on the last lap… Gardner's the fastest of the race.
Raul Fernandez lost touch in the end but it was nevertheless a phenomenal ride from the rookie to claim his maiden Moto2™ podium, turning promise last weekend to an even bigger delivery of results this time out. Bezzecchi eventually had a lonely ride home to P4 and a podium evades one of the pre-season favourites, but the Italian has never loved Doha.
Behind that leading quartet, rookie Ai Ogura (Idemitsu Honda Team Asia) put in a stunner as he shot up the timesheets second time out in Moto2™. Battling with the best of them, the Japanese rider just beat Augusto Fernandez (Elf Marc VDS Racing Team) to fifth place and will now have his sights set on even more in Portimao. Augusto Fernandez, after a tougher start to the year, will also be happier with a top six.
Yet another rookie in the form of Celestino Vietti (Sky Racing Team VR46) picked up a second consecutive point-scoring ride, taking an impressive P7. Stefano Manzi (Flexbox HP40) was just 0.029s behind his fellow VR46 Academy member in P8, with Xavi Vierge (Petronas Sprinta Racing) picking up a P9 from P19 on the grid. He beats 10th place Fabio Di Giannantonio (Federal Oil Gresini Moto2) by six tenths as Diggia faded after an initial charge.
Rookie Tony Arbolino (Liqui Moly Intact GP) was 11th for his first Moto2™ points, and the Italian led Bo Bendsneyder (Pertamina Mandalika SAG Team), Jorge Navarro (MB Conveyors Speed Up), Lorenzo Dalla Porta (Italtrans Racing Team) and reigning Moto3™ World Champion Albert Arenas (Solunion Aspar Team) over the line as they completed the points.
Cameron Beaubier (American Racing), Tom Lüthi (Pertamina Mandalika SAG Team) and Aron Canet crashed out on their own, with Jake Dixon (Petronas Sprinta Racing) and Marcel Schrötter (Liqui Moly Intact GP) crashing out together at the final corner. Joe Roberts (Italtrans Racing Team) also crashed out from the battle behind the top four.
So it's a maximum of 50 points for Lowes at Losail, the perfect start to 2021. But Gardner is just 10 points behind him in the standings after two P2 and next, we're heading for Portimao – scene of Gardner's first Grand Prix victory in 2020…
Sam Lowes: "It was nice, after the crash in Warm Up, again… the pace was great, the first couple of laps when I was behind it felt really easy in Sector 3 to follow because of the wind, it was easy to stay behind but when I got to the front it was hard to pull away because of the wind. I just tried to stay consistent and save a bit of tyre for the end of the race. The last 3 or 4 laps I pushed and and my pace was real fast, I think Remy got the best lap on the last lap but I got it first and him by trying to beat me! Overall I'm very happy, we've done a great job these weeks in Qatar, everyone caught up in the second weekend, which is normal. They're very talented these guys so when you have a margin after a few weeks it gets smaller and smaller. But mentally for me it was a great race to lead like that and I can go to Portimao with good feeling."
More, from a press release issued by Italtrans Racing:
Joe Roberts crashes out on race day in Doha.
Lorenzo Dalla Porta finishes in the points.
After last week's first GP the MotoGP World Championship remains in Qatar for the Doha Grand Prix, second round of the season. Bittersweet race for Italtrans Racing Team.
Good performance for Lorenzo Dalla Porta, who gets the first points in his second season in Moto2. 24th on the grid, the Tuscan rider immediately set a good pace, recovering positions lap after lap finishing 14th.
Unlucky Sunday for Joe Roberts. After a great laptime in the warm up with the 4th position, in race the American rider crashed after only six laps while he was 5th and was pushing to catch the front group and fight for the podium.
Lorenzo Dalla Porta
"Today we get the first points of the season. It's not the result we are aiming for, but it's a good starting point, especially considering how the weekend and the last race went. I'm partly happy and confident in view of the next Grand Prix. I thank all the guys who are working so hard".
Joe Roberts
"I have been unfortunate into a promising race. I really felt we had the pace to be up there battling in the front. I did not have a great start but I felt confident that I could catch the front group. Unfortunately, I made a mistake. Anyway, we learned a lot this weekend and the team and me were still working very well together".
Giovanni Sandi – Technical Director:
"The race didn't finish as we had hoped, but we are competitive and our potential is high. The guys showed they can do well: Joe was fighting for the top positions, while Lorenzo made a good comeback. We are ready to continue working in view of the GP in Portimao".
More, from a press release issued by American Racing Team:
Cameron Beaubier falls fighting for Moto2 points in Qatar
American Racing heads to Europe for third round of world championship
DOHA, Qatar (April 4, 2021) — American Racing rider Cameron Beaubier crashed on Sunday in the Grand Prix of Doha, the second of two FIM Moto2 World Championship races at the Losail International Circuit in Qatar.
The 28-year-old Californian qualified 14th out of 28 riders for the 20-lap race under the floodlights at the 16-turn, 3.34-mile Gulf state circuit, which opened in 2004.
Weather conditions improved overnight. Ambient temperature at race time was 70 degrees Fahrenheit, with an 9-mph breeze.
Beaubier lost two positions at the start and slipped further downfield in the opening laps. He battled to 13th before falling in Turn 7 with 12 laps remaining. Beaubier posted the second highest top speed of the race, 180.392 mph.
Marc VDS rider Sam Lowes started from pole position for the second consecutive weekend. Lowes took the lead on the fourth lap and earned a narrow victory ahead of Red Bull KTM Ajo's Remy Gardner.
Beaubier finished 11th a week ago at Losail in the opening race of the season. The five-time MotoAmerica Superbike champion is 17th overall in the championship points standings.
Beaubier's teammate, Marcos Ramirez, did not ride this weekend. The 23-year-old Spaniard crashed in qualifying for the opening round and was unfit to race at the second round, as well.
The American Racing Team will return to action in two weeks, April 16-18, at the Algarve International Circuit for the Grand Prix of Portugal.
About the American Racing Team
The American Racing Team is owned by Avner Kass and Eitan Butbul and competes in the FIM MotoGP World Championship. Based in California, the team fields two riders in the Moto2 class: American Cameron Beaubier (No. 6) and Spaniard Marcos Ramirez (No. 42). American Racing has grown under Butbul's guidance and is a respected member of the MotoGP paddock.
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Students enroll in two courses.
This course will explore the rich art and architecture of Florence and its surrounding cities. Students will attend seminars at the Middlebury College Center situated in the heart of Florence. The class will also include visits to many of the area's museums and field trips to surrounding cities.
Beginning with the Congress of Vienna, this course examines Italy's tumultuous path toward nationhood and unification, known as the Risorgimento. We will consider the ways in which, though politically unified, the peninsula remained economically, socially, culturally, and linguistically divided in the decades that followed. While this course studies Italian unification from a historical perspective, readings are interdisciplinary in nature and include excerpts from Giuseppe Tomasi di Lampedusa's The Leopard (Il Gattopardo), Antonio Gramsci's Prison Notebooks (Quaderni del carcere), and the operas of Giuseppe Verdi. Of course, particular attention is given to Florence and the region of Tuscany: from the Macchiaioli painters to Florence's short-lived status as the nation's capital and the election of the Florentine dialect as the basis of what eventually became standard Italian.
Spread out along the Arno River, Florence boasts a medieval historic center surrounded by beautiful hills and vistas. Although smaller than most major cities, Florence offers all the culture and vitality of a key metropolis. Its extraordinary past—from Etruscan village, to small Roman outpost, to Renaissance center, to capital of united Italy, to modern European city—offers palpable immersion in an age-old civilization. Life in Florence offers a unique opportunity to inhabit history while enjoying a vibrant, modern city.
While in Florence, students live in an Italian home. Homestay hosts are native Italians who welcome students to share their home, meals, and conversations.
Homestay includes breakfast and dinner five days a week. Students are responsible for weekend meals unless provided by program.
Please note: Students are responsible for their own travel costs to and from Florence, Italy.
Art history faculty member Joseph Forte, who leads the Summer in Florence program, was interviewed for the Italian television series Americans in Love with Italy. Get to know him by watching the video below, and don't hesitate to e-mail him for more information on the Summer in Florence Program!


text:
Hearat Shulayim (), internationaler Titel Footnote, ist eine israelische Filmkomödie von Joseph Cedar aus dem Jahr 2011.

Handlung
Professor Eliezer Shkolnik beschäftigt sich wie sein Sohn Uriel mit Talmudstudien an der Hebräischen Universität Jerusalem. Im Gegensatz zu seinem Sohn, der beliebt ist, rege publiziert und immer wieder auch Auszeichnungen erhält, hatte Eliezer über viele Jahre an seinem Lebenswerk gearbeitet und nicht publiziert. Seine Entdeckung nach vielen Jahren akribischer Forschung sollte in einer großen Publikation münden. Kollege Yehuda Grossmann durchkreuzte die Pläne und veröffentlichte Eliezers Entdeckung basierend auf eigenen Erkenntnissen kurz vor dessen geplanter Publikation selbst. Auch wenn Eliezer auf seinem Gebiet als Experte gilt, erholte er sich von diesem Rückschlag nie ganz. Den Israel-Preis, auf den er jedes Jahr hofft, hat er noch nie bekommen, obwohl er seit 16 Jahren immer nominiert war. Da Intimfeind Grossmann in der Jury sitzt, wird Eliezer den Preis auch nie bekommen – Grund genug für Eliezer, seit Jahren die Preisträger öffentlich als Scharlatane und Nichtskönner zu beschimpfen und sich selbst misanthropisch zurückzuziehen. Auch das Verhältnis zu Sohn Uriel verschlechtert sich, sieht Eliezer jeden Erfolg des inzwischen selbst als Professor lehrenden Uriel als Affront gegen sich an.

Eines Tages erhält Eliezer einen Anruf vom Erziehungsministerium, dass er in diesem Jahr den Israel-Preis erhalten wird. Eliezer ist überrascht und erfreut und auch der Rest der Familie zeigt sich nach anfänglicher Zurückhaltung erleichtert, dass das Lebenswerk des Ehemanns und Vaters nun doch noch anerkannt wird. Uriel wiederum wird – nachdem auch die Zeitung Hareetz die Verleihung an Eliezer bekanntgegeben hat – ins Ministerium gebeten. Durch eine Verwechslung habe man Eliezer am Telefon vom Preiserhalt berichtet und nicht dem eigentlichen Preisträger – Uriel. Uriel ist verblüfft, macht jedoch nach kurzer Zeit klar, dass man Eliezer den Preis nicht rückwirkend wieder wegnehmen könne. Dies würde ihn umbringen. Als Grossmann auf einer Auszeichnung Uriels besteht, wird dieser laut und bezichtigt Grossmann, seinen Vater nur aufgrund persönlicher Animositäten nie den Preis verliehen zu haben. Er wisse, dass Eliezer seit 16 Jahren nominiert war, da er ihn selbst jährlich vorgeschlagen habe. Der Streit wird handgreiflich. Am Ende willigt Uriel ein, seinem Vater vom Fehler zu berichten, ändert seine Meinung jedoch, als er Eliezer mit Kollegen die Auszeichnung feiern sieht. Im persönlichen Gespräch mit Grossmann macht Uriel deutlich, dass eine Aberkennung des Preises nicht zuletzt zu einem endgültigen Bruch zwischen ihm und seinem Vater führen würde. Grossmann willigt schließlich ein, Eliezer auszuzeichnen, stellt jedoch zwei Bedingungen: Uriel muss die Auszeichnungsbegründung der Jury schreiben, sei Eliezers einziges Vermächtnis doch, dass er in einer Fußnote eines Werks seines Lehrers Feinstein genannt werde. Zudem könne Uriel beim Verzicht auf die Auszeichnung nie selbst mit dem Israel-Preis ausgezeichnet werden. Uriel stimmt den Bedingungen zu.

Er schreibt die Jurybegründung, die ihm schwerfällt. Eliezer gibt unterdessen Hareetz ein Interview, in dem er vor allem die wissenschaftliche Arbeit seines Sohnes als oberflächlich kritisiert und ihnen das Recht, "Talmudstudien" genannt zu werden, abspricht. Uriel ist empört und lässt seine schlechte Laune an Studenten, seiner Frau und seinem Sohn aus. Während einer Theateraufführung gesteht er schließlich seiner Mutter, dass eigentlich er den Preis erhalten sollte, trotz Verwechslung jedoch auf der Auszeichnung seines Vaters bestanden habe. Seine Mutter leidet nun im Stillen mit ihm, verrät jedoch nichts. Eliezer erkennt unterdessen, dass die Jurybegründung in einer merkwürdigen Kombination das Wort  (Hochburg) verwendet, das immer wieder in Schriften seines Sohnes erscheint. Grossmann, der die Jurybegründung unterschrieben hat, verwendet es jedoch nie. Auch andere Wortkombinationen verweisen darauf, dass Uriel der Verfasser der Jurybegründung ist. Zudem bemerkt Eliezer, dass beim Telefonat mit dem Erziehungsminister nie sein Vorname genannt wurde. Ein zwangloses Treffen im Vorfeld der Verleihung, auf das die Ministerin verwies, bezieht sich auf eine Konferenz, auf der Uriel reden sollte. Eliezer ist konsterniert, verfolgt den Tag der Verleihung sprachlos, lässt die Generalprobe im International Convention Center Jerusalem wortlos über sich ergehen und wartet schließlich angespannt mit den anderen Preisträgern hinter der Bühne, während die Verleihungszeremonie beginnt.

Produktion

Hearat Shulayim war der vierte Spielfilm von Regisseur Joseph Cedar. Cedar studierte Philosophie und Theatergeschichte an der Hebräischen Universität Jerusalem; sein Vater ist der Israel-Preisträger Howard Cedar. Cedar gab an, dass die Filmidee auf etwas basiert, das ihm selbst beinahe zugestoßen wäre ("It is remotely based on something that almost happened to me") und dass er sich im Film ausmalte, wie sich die Situation weiterentwickelt hätte. Das Institut für Talmudforschung der Hebräischen Universität Jerusalem sei wiederum ein "bemerkenswerter Ort", voller Rivalität zwischen Professoren, die wiederum sehr exzentrisch seien, sodass er sich in jeden einzelnen von ihnen verliebt habe und sie zum Mittelpunkt seines Films machte.

Hearat Shulayim wurde in Jerusalem gedreht. Als Drehorte dienten unter anderem das International Convention Center Jerusalem und die Hebräische Universität Jerusalem. Die Kostüme schuf Laura Sheim, die Filmbauten stammten von Arad Sawat. An der Finanzierung des Films beteiligten sich unter anderem der Israel Film Fund, der Jerusalem Film and Television Fund und die Avi-Chai-Stiftung. Der Film markierte nach langer Abstinenz die Rückkehr von Shlomo Bar-Aba auf die Kinoleinwand; sein letzter Kinofilm Kvalim stammt aus dem Jahr 1992.

Der Film erlebte am 14. Mai 2011 im Rahmen der Internationalen Filmfestspiele von Cannes seine Premiere. In Israel lief er am 25. Mai 2011 in den Kinos an. In Deutschland wurde der Film auf Festivals gezeigt, darunter 2013 im Rahmen der 4. Jüdischen Filmtage München.

Auszeichnungen (Auswahl)
Joseph Cedar erhielt in Cannes 2011 den Preis für das Beste Drehbuch. Hearat Shulayim lief zudem im Wettbewerb um die Goldene Palme. Der Film erhielt 2011 insgesamt zehn Ophir Awards und war für drei weitere Preise nominiert. Das National Board of Review zählte Hearat Shulayim zu den besten fünf Filmen des Jahres 2011.

Als Gewinner des Ophir Awards für den Besten Film wurde Hearat Shulayim automatisch Israels Beitrag zur Oscarverleihung 2012. Er setzte sich im Vorfeld durch und wurde 2012 für einen Oscar in der Kategorie Bester fremdsprachiger Film nominiert. Zudem erhielt er eine Nominierung für einen Independent Spirit Award für das beste Drehbuch.

Weblinks

Einzelnachweise

Filmtitel 2011
Israelischer Film
Filmkomödie

redpajama_set_name: RedPajamaWikipedia


text:
Keeping the stock safe: An inside look at the vets helping Steamboat Springs Pro Rodeo animals
Sports | May 31, 2019
Eugene Buchanan
Dr. Louise Batt cares for a horse.
High Country Vet Services' Dr. Marianne Marshall, is a certificated veterinary chiropractor and acupuncturist.
STEAMBOAT SPRINGS — While every effort is made to keep the cowboys and cowgirls safe at Romick Arena during the Steamboat Springs Pro Rodeo Series, the same holds true for the animals the audience sees performing.
Just like the ambulance that remains on-site for the contestants' safety, a custom Dodge truck nearby provides the same service for the horses and livestock.
"It's our mobile vet unit," said Dr. Louise Batt of High Country Vet Services, which is entering its third year of providing high quality veterinary services for the rodeo's animals. "It has everything we need to care for them, including digital X-ray equipment."
Raised in England, Dr. Batt moved to Steamboat in 2013 from Cañon City, where she cared for wild mustangs for the Bureau of Land Management and bucking bulls for rodeo stock producers such as Mike Hadley. Since then she's built High Country Vet Services into a thriving operation focusing on competition horses and livestock.
"We focus on equine sports medicine, lameness investigation and beef herd management," said Dr. Batt, whose practice offers state-of-the-art mobile diagnostic equipment, the latest treatment options available, as well as a facility for hospitalizing horses and handling cattle.
While caring for rodeo animals is second nature for her and fellow practitioner Dr. Marianne Marshall, a certificated veterinary chiropractor and acupuncturist, it's different than a typical farm visit.
"We walk through the pens beforehand to make sure none of the animals are sick or hurt and care for any injuries," she said. "We also help the riders' horses. And if for some reason they forgot their vet certificates for their next rodeo, we can issue those, too."
The bottom line is the animals are cared for as much as the competitors.
"It's great fun," said Dr. Batt. "Luckily, there haven't been too many hiccups so far."


Nigel Baines a past president and former Rushmoor councillor passed away.
Nigel was President of Farnborough Rotary club from 2005-2006.
He had suffered with illness for the last couple of years.
One of Nigel's favourite charities was Farnborough-based Parity For Disability.
He took part in many fund raising activities for Parity, including walking on hot coals and scaling large buildings, despite being in his late 60's.
Nigel always somebody I looked up to (still do), initially my manager and later a good friend. A thoroughly decent, honorable man for whom I have much to thank.
I miss our chats Nigel, bye for now and see you later.
Farnborough Rotary Club © 2012. All rights reserved.


text:
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	intent.putExtra('interval', 180000);
	// A message that the service should 'echo'
	intent.putExtra('message_to_echo', 'Titanium rocks!');

	var service = Titanium.Android.createService(intent);
	service.addEventListener('resume', function(e) {
		Titanium.API.info('Service code resumes, iteration ' + e.iteration);
	});
	service.addEventListener('pause', function(e) {

		//    Titanium.API.info('Service code has run 3 times, will now stop it.');
		//service.stop();

	});
	if (!Ti.Android.isServiceRunning(intent)) {
		Ti.API.warn('Service not running ... Starting now!');
		Ti.Android.startService(intent);
	} else {
		Ti.Android.stopService(intent);
		Ti.API.warn('Service was running, now STOPPED  ... Starting again now!');
		Ti.Android.startService(intent);
	}

	//service.start();
	return;
};
module.exports = START;

redpajama_set_name: RedPajamaGithub


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text:
HomeBreaking NewsAmnesty urges ICC to probe 'crimes against humanity' in Venezuela – Aljazeera.com
Amnesty urges ICC to probe 'crimes against humanity' in Venezuela – Aljazeera.com
May 15, 2019 Noticias de Nueva Esparta Venezuela Breaking News, Internacionales, Venezuela, Venezuela News 0
Amnesty International said on Tuesday it believes the Venezuelan authorities have committed crimes against humanity in their crackdown on anti-government protests, and urged the International Criminal Court (ICC) to investigate.
The rights group said President Nicolas Maduro's government responded with "a systematic and widespread policy of repression" in late January, when anti-government protests swept the country after opposition leader Juan Guaido invoked the constitution to declare himself interim president, declaring Maduro's 2018 re-election illegitimate.
Maduro opponents were tortured and killed during the protests, Amnesty said.
"The nature of the attacks … the level of coordination by the security forces, as well as the signs of similar patterns in 2014 and 2017, leads Amnesty International to believe that the Venezuelan authorities committed crimes against humanity," Amnesty said in a statement.
Guaido is locked in a bitter power struggle with Maduro, who maintains the support of Russia, China and Turkey, as well as most of the country's institutions, including the military. He accuses Guaido and the United States of attempting a coup.
Guaido, the leader of Venezuela's opposition-controlled legislature, declared himself acting president on January 23. The opposition leader has since been recognised by more than 50 countries, led by the US.
Amnesty sent a fact-finding mission to Venezuela in February to research the crackdown on the anti-government protests that preceded and followed Guaido's swearing-in.
Torture, executions
The London-based rights group said at least 47 people were killed during the protests from January 21 to 25. At least 33 were shot dead by the security forces, and six by government supporters.
"Eleven of these deaths were extrajudicial executions," said Erika Guevara, Americas director for Amnesty International, who presented the report in Mexico City.
"State forces identified people who had been prominent in the protests in their communities, located them and shortly afterwards killed them … Some of them were tortured before they were killed," the report said.
More than 900 people, including children, were arbitrarily detained over the same period, it said.
It called on the UN Human Rights Council and ICC to investigate.
Amnesty's team found that crimes and human rights violations were committed in "an attack planned and led by the security forces against individuals identified as or perceived to be opponents, particularly in impoverished areas."
Maduro himself "knew about these public and appalling acts and took no measures to either prevent or investigate them," it said.
Maduro's government has not responded to the allegations.
Millions of Venezuelans have fled Venezuela in recent years as the country experiences hyperinflation, unemployment and food and medicine shortages.
Security forces block opposition politicians
Meanwhile on Tuesday, Venezuelan security forces prevented opposition politicians from entering the parliament building for a session on Tuesday, a week after the top court stripped several politicians of their immunity.
Members of the Sebin intelligence service, wearing masks and carrying long guns, together with members of the national police and the military blocked the entrance and were investigating the possible presence of an explosive device inside the National Assembly building, politicians said.
Last week, one opposition politician was arrested and several took refuge in foreign embassies in Caracas or fled the country
"This is all part of a show to prevent the National Assembly from functioning," politician Juan Pablo Guanipa told Reuters News Agency. "This is a dictatorship that goes after dissidents, and we are fighting for a political change."
On Tuesday, the Supreme Tribunal accused four opposition legislators of treason and conspiracy, according to a statement posted on the court's Facebook page, following similar earlier accusations against 10 opposition politicians.
The moves come after opposition politicians participated in demonstrations that were part of a failed uprising led by Guaido on April 30.
Venezuela's information ministry, which handles media inquiries on behalf of the government, did not immediately respond to a request for comment.
The government stripped the assembly of most of its powers after the opposition won a majority in 2015 elections. Politicians loyal to Maduro generally do not attend the sessions, but go to meetings of the constituent assembly, a legislative "superbody" created in 2017 that meets in the same building on Wednesdays.
Tuesday's session was scheduled for 10am (14:00GMT), but never began. The politicians were set to discuss the Supreme Tribunal's stripping of several of their colleagues' parliamentary immunity and the arrest of Edgar Zambrano, the National Assembly's vice president and an outspoken critic of Maduro.
Opposition politician Jorge Millan told reporters the report of "bombs" in the building was false.
"It is a trick to prevent the parliament from functioning today," he said. "If we do not have a session today, we will do it tomorrow."
Chinese cargo plane arrives in Venezuela – CNN
Maduro's 'collectivos' strike terror while trying to win back support of Venezuela's most vulnerable – Fox News
Lula da Silva recibe título de Ciudadano Honorario de París
October 4, 2019 Noticias de Nueva Esparta Venezuela 0
El expresidente de Brasil, Luiz Inacio Lula da Silva, quien permanece en prisión desde abril de 2018, recibió el jueves el título de Ciudadano Honorario de París. LEA TAMBIÉN: Lula reitera su inocencia y confianza […]
Venezuela Struggles to Pump, Ship Oil After U.S. Sanctions – The Wall Street Journal
February 5, 2019 Noticias de Nueva Esparta Venezuela 0
CARACAS, Venezuela—Venezuelan crude exports are declining sharply as new U.S. sanctions push the country's oil industry closer to collapse, threatening a bigger impact on global markets than many experts anticipated, people familiar with the matter […]
Russia in Venezuela: Why Vladimir Putin has sent troops to back up Nicolas Maduro as the Trump administration backs Juan Guaido – CBS News
April 5, 2019 Noticias de Nueva Esparta Venezuela 0
Moscow – Venezuela is not going to become "another Syria" for Moscow, Russian Foreign Minister Sergey Lavrov told a state-backed Russian newspaper in an interview published this week. "We have nothing to hide," he said in response […]