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Research ArticleCHEMICAL PHYSICS
Conical intersection–regulated intermediates in bimolecular reactions: Insights from C(1D) + HD dynamics
View ORCID ProfileYanan Wu1,2,*,
View ORCID ProfileJianwei Cao1,*,
Haitao Ma1,
Chunfang Zhang1,3,
View ORCID ProfileWensheng Bian1,2,†,
View ORCID ProfileDianailys Nunez-Reyes4,5 and
View ORCID ProfileKevin M. Hickson4,5,†
1Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
2School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
3College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China.
4Université de Bordeaux, Institut des Sciences Moléculaires, F-33400 Talence, France.
5CNRS, Institut des Sciences Moléculaires, UMR 5255, F-33400 Talence, France.
↵†Corresponding author. Email: bian{at}iccas.ac.cn (W.B.); kevin.hickson{at}u-bordeaux.fr (K.M.H.)
↵* These authors contributed equally to this work.
Science Advances 26 Apr 2019:
Vol. 5, no. 4, eaaw0446
Yanan Wu
ORCID record for Yanan Wu
Jianwei Cao
ORCID record for Jianwei Cao
Haitao Ma
Chunfang Zhang
Wensheng Bian
ORCID record for Wensheng Bian
For correspondence: bian@iccas.ac.cn kevin.hickson@u-bordeaux.fr
Dianailys Nunez-Reyes
ORCID record for Dianailys Nunez-Reyes
Kevin M. Hickson
ORCID record for Kevin M. Hickson
The importance of conical intersections (CIs) in electronically nonadiabatic processes is well known, but their influence on adiabatic dynamics has been underestimated. Here, through combined experimental and theoretical studies, we show that CIs induce a barrier and regulate conversion from a precursor metastable intermediate (CI-R) to a deep well one. This results in bond-selective activation, influencing the adiabatic dynamics markedly in the C(1D) + HD reaction. Theory is validated by experiment; quantum dynamics calculations on highly accurate ab initio potential energy surfaces yield rate coefficients and product branching ratios in excellent agreement with the experiment. Quasi-classical trajectory calculations reveal that the CI-R intermediate leads to unusual reaction mechanisms (designated as C─H activation complex conversion and cyclic complex), which are responsible for large branching ratios. We also reveal that CI-R intermediates exist in other reactive systems, and the dynamical effects uncovered here may have general significance.
Conical intersections (CIs) are important in many chemical and biological systems (1–7), ranging from elementary reactions involving three to five atoms (4, 5) to biomolecules such as DNA (6) and proteins (7). In particular, CI-induced ultrafast nonadiabatic dynamics have attracted substantial interest over the past two decades (7–11). In contrast, the effects of CIs in adiabatic reaction dynamics have been mostly neglected when nonadiabatic effects are small. Here, we find that the CI between the b∼A′′1 and d∼A′′1 states in the C(1D) + HD reaction (Fig. 1A) induces a small barrier and a shallow precursor well (Fig. 1B) before the deep well on the lower potential energy surface (PES). These features have a profound effect on the adiabatic reaction dynamics. The shallow well supports a metastable-state complex corresponding to a cyclic CHD structure, whose stability is regulated by the CI-induced barrier, and thus, it is designated as a CI-regulated (CI-R) intermediate here. We further reveal that the CI-R intermediate triggers bond-selective activation through two unusual reaction mechanisms and has a strong influence on product branching ratios of the C(1D) + HD reaction. These findings are achieved through combined experimental and theoretical studies, including low-temperature experiments using a supersonic flow reactor and extensive dynamical calculations on highly accurate ab initio PESs. These results are important for acquiring a deeper understanding of complex-forming reactions and may provide us with a potential method to control chemical reactions by adjusting the location of CIs with lasers.
Fig. 1 Schematic reaction profile and C2v conical interaction.
(A) The b∼A′′1 potential profile along the reaction path for the C(1D) + HD reaction. MECP, minimum energy crossing point. (B) A two-dimensional view of the C2v CI between the b∼A′′1 and d∼A′′1 states. All indicated values and potentials are from our ab initio calculations, the details of which along with those about the g-h coordinates are given in the Supplementary Materials. The CI-R metastable-state intermediate is shown. The bond lengths are in bohr, and the angles are in degrees.
It is well known from the current understanding of chemical reactions that the transition state determines the rate coefficient of a direct-activated reaction, whereas the deep well intermediate complex dominates that of a complex-forming reaction, forming the basis of many approximate theories of chemical reaction rates. Here, we demonstrate a more complicated and interesting case, in which a precursor intermediate plays an important role and traditional approximate theories fail. This case involves multiple maxima and minima in the PES, presenting "the most severe challenge" (12) to PES construction and quantum dynamics (QD) calculations (13).
Extensive experimental and theoretical efforts have been devoted to the C(1D) + H2 reaction and its isotopic variants. Experimentally, several kinetic and dynamical measurements (14–19) have been reported. In particular, Fisher et al. (14) and Sato et al. (15) measured the CD/CH branching ratio of the C(1D) + HD reaction through pump-probe techniques. Moreover, intramolecular isotopic effects in A + HD–type insertion reactions under crossed beam or thermal conditions have been discussed by Liu (16). Recently, Hickson et al. (18, 19) measured low-temperature rate coefficients for the C(1D) + H2 (D2) reactions using the supersonic flow reactor technique. Theoretically, Bussery-Honvault et al. (20) were the first to develop a global ab initio PES [called Bussery-Honvault–Honvault-Launay (BHL)] for the a∼A′1 state; the ab initio data were subsequently refitted with the reproducing kernel Hilbert space method (RKHS PES) (21). Later, Joseph and Varandas (22) developed a double many-body expansion a∼A′1 PES. These surfaces have since been used in various dynamical calculations (17–25). More recently, a highly accurate global ab initio PES (or ZMB-a) has been constructed by Bian's group (26), which is unique in the accurate description of the regions around CIs and van der Waals interactions, and further dynamical calculations (27, 28) have been performed on this PES. For the b∼A′′1 state, a global ab initio PES [called Bussery-Honvault–Julien–Honvault-Launay (BJHL)] has been constructed by Bussery-Honvault et al. (29). This surface has been applied in the most recent studies (19), although the inclusion of contributions from the BJHL surface worsens the agreement between theory and experiment (17), indicating its probable deficiency. In contrast, the use of a b∼A′′1 PES newly constructed by Bian's group has notably improved the agreement with crossed beam experiments (30).
Points of the C2v intersection between the b∼A′′1 and d∼A′′1 states are continuously connected, thus forming a seam line. The minimum energy crossing point (MECP) is determined by our ab initio calculations, with its geometry and energy indicated in Fig. 1A, and evidence that this intersection is conical is presented in Fig. 1B, fig. S1, and Supplementary Text. Figure 1 shows that the CI between the b∼A′′1 and d∼A′′1 states induces a barrier-like structure, which regulates the dissociation of a highly bent precursor intermediate supported by a shallow well (−14.37 kcal/mol relative to the reagent asymptote). The corresponding results of geometry optimization and frequency analysis are given in table S1. It is still unclear how this type of CI-R intermediate influences the reaction dynamics, and we will reveal its important role below.
The b∼A′′1 PES (hereafter called ZMB-b) constructed by Bian's group provides an accurate description of the regions around the C2v CI (see fig. S2 and Supplementary Text), and an adjusted b∼A′′1 PES (hereafter called ZMB-bt) is also constructed for comparison (see below and fig. S2D). To fully characterize the role of the CI-R intermediate, we have performed extensive dynamical calculations on the ZMB-a, ZMB-b, and ZMB-bt PESs for the C(1D) + HD reaction. The C(1D) + HD isotopomer of the reactive system is chosen, since the CD/CH branching ratio is a sensitive probe of the PES topology and dynamics. These calculations are supported by our measurements (fig. S3) of the temperature-dependent rate coefficients and product branching ratios for both channels of the title reaction using a supersonic flow reactor over the temperature range of 50 to 296 K. Descriptions of the experimental and theoretical methodologies are provided in Materials and Methods and in the Supplementary Materials.
Figure 2A shows the experimental and theoretical rate coefficients as a function of temperature, where the exact time-dependent wave packet method including contributions from all angular momenta J (fig. S4) is used to perform QD calculations on the ZMB-a and ZMB-b PESs for the C(1D) + HD (v = 0, j = 0) reaction. Calculated initial state-specified rate coefficients are in excellent general agreement with the measured values, and both results present a slightly negative temperature dependence in the temperature range of 100 to 300 K. Although the calculated state-specified rate coefficient is slightly higher than the experimental one at room temperature, this can be attributed to the effects of higher HD initial rotational states, which will be discussed below.
Fig. 2 Comparison of experimental and theoretical results.
(A) The rate coefficients and (B) CD/CH product branching ratios as a function of temperature for the C(1D) + HD reaction. Accurate QD calculations are performed on the ZMB-a (a∼A′1) and ZMB-b (b∼A′′1) PESs. The QD result on the BHL and BJHL surfaces is from (25), whereas the experimental result is from Fisher et al. (14).
Figure 2B shows the measured CD/CH product branching ratios alongside the calculated results on different PESs. The branching ratios derived by our QD calculations on the ZMB-a and ZMB-b surfaces are in excellent agreement with the experimental data at 50, 75, and 127 K, although a larger difference is observed at 298 K; a fact that could be due to the participation of higher HD(j) states at temperatures above 150 K. As the present QD calculations are too computationally expensive to take into account these higher HD rotational states, we performed quasi-classical trajectory (QCT) (31) calculations instead to elucidate the effects of j excitation on the calculated rate coefficients and branching ratios at 298 K. The QCT results show that the inclusion of higher HD rotational states lowers the branching ratio by 0.12, thereby reducing the difference between theory and experiment at this temperature. In addition, earlier experiments by Fisher et al. (14) yield a CD/CH ratio of 1.7 at room temperature, which is somewhat closer to our calculated value as shown in Fig. 2B. The QCT calculations also indicate that the calculated thermal rate coefficient at 298 K is slightly smaller when j excitation is included, bringing the theoretical results more into line with the experimental ones. The results from our QCT and QD calculations are compared in table S2, indicating that the two kinds of calculations are generally consistent with each other.
We also see from Fig. 2B that, at 127 K, the branching ratio from calculations on the BHL and BJHL PESs is close to that on the single ZMB-a surface and is lower than the measured value, whereas the agreement with the experiment achieved on the ZMB-a and ZMB-b surfaces is excellent below room temperature. Reaction over the ZMB-b surface yields very large CD/CH branching ratios (also see Table 1), a phenomenon that can be ascribed to the influence of the CI-R intermediate (Fig. 1A). Evidence is provided below describing the role of this intermediate species.
Table 1 Rate coefficients and CD/CH product branching ratios.
QCT and QD results on the ZMB-b and ZMB-bt surfaces for the C(1D) + HD (v = 0, j = 0) reaction are presented.
To demonstrate the dynamical effect of the shallow well on the ZMB-b surface, we have constructed the ZMB-bt surface, which is identical to the ZMB-b one, except that the cyclic structure shallow well is removed. So the ZMB-bt surface omits the precursor well that supports the CI-R intermediate. We perform QCT and QD calculations on the ZMB-bt surface, and the rate coefficients and branching ratios obtained are summarized in Table 1, along with those obtained on the ZMB-b surface. The CD/CH branching ratios obtained from the ZMB-b surface are much larger than those from the ZMB-bt surface, although the rate coefficients obtained from both surfaces are very similar. It is clear that the CI-R shallow well plays the key role. Moreover, the CD/CH branching ratios from ZMB-b are also much larger than those from the BJHL surface, and this may be caused by the inadequate description of the CI-R barrier and shallow well on the BJHL surface (see the Supplementary Materials).
Table 1 also shows that the present QCT and QD results on the ZMB-b and ZMB-bt surfaces accord well, although the QCT method is more sensitive to the existence of the CI-R shallow well, leading to a more pronounced increase in the branching ratio. This justifies the following analysis with the QCT method, which is used to further account for the much larger branching ratios on ZMB-b than on other PESs below room temperature. Reactive classical trajectories on ZMB-b are compared with trajectories from the same initial conditions on other PESs. We find that the CI-R intermediate leads to unusual reaction mechanisms with obvious nonstatistical features.
We distinguish the newly found mechanisms into two types: Type I is designated as the C─H activation complex conversion mechanism, whereas type II is the cyclic complex mechanism (see the Supplementary Materials for details). At 0.01 eV collision energy, the type I mechanism dominates, accounting for 83% of all reactive trajectories. The main feature of the type I mechanism is that the C─H bond is selectively stretched or activated when the system leaves the shallow well region (before entering the deep well region). We attribute this selective activation of the C─H bond to two factors. First, the nascent cyclic complex has a large-amplitude C─H stretch vibrational mode (fig. S5A and table S1). Second, as shown in Fig. 1B, the top of the CI-induced barrier has a C2v symmetry, allowing the interaction potential to divert the system from the isosceles geometries. This effect helps to orient the C atom closer to the D atom before the system enters the deep well, promoted by the bending mode of the cyclic complex (fig. S5B).
The type I mechanism can be further divided into two submechanisms, C─H preactivation and reactivation ones, and their difference is that reactivation trajectories undergo at least one C─H bond reactivation by traveling back to the shallow well from the deep well before dissociation. The ratio between the former and latter mechanisms is about one-half at 0.01 eV. To illustrate the type I mechanism, snapshots of a typical reactive trajectory undergoing a simple C─H preactivation complex conversion are shown in Fig. 3. When the reagent C atom approaches the HD molecule, the reagents initially form an intermediate species bound by the shallow well, followed by a rapid increase in the H─D distance. Since the lighter H atom moves much faster than the heavier D atom, the newly formed C─H bond is notably longer than the C─D bond, leading to the formation of one highly activated (excited) bond (C─H) and one inactivated bond (C─D) before the trajectory enters the deep well region. Here, C─H bond activation is retained as the intermediate bends and inverts before dissociating into CD + H. Note that Fig. 3 shows a simple direct mechanism, accounting for only 8% of the C─H preactivation complex conversion mechanism. While many other reactive trajectories (92%) remain longer in the deep well before dissociating (fig. S6A), our analysis indicates that C─H activation is retained for more than 40% of these indirect trajectories. The C─H preactivation mechanism is beneficial for the formation of CD + H products and a correspondingly large CD/CH branching ratio. Actually, in the type I mechanism, the C─H reactivation submechanism dominates, and it is common for long-lived trajectories on ZMB-b to travel back and forth between the shallow and deep well regions (fig. S6B). Approximately half of the C─H reactivation trajectories preserve C─H bond activation before dissociation, which promotes CD + H formation.
Fig. 3 Revealing the C─H bond activation process.
(A) Snapshots of a typical reactive trajectory and (B) the corresponding internuclear distance and potential energy variations as a function of time. The trajectory is undergoing the type I mechanism and is calculated at 0.01 eV collision energy for the C(1D) + HD (v = 0, j = 0) reaction on the ZMB-b surface.
The type II mechanism also favors CD + H formation. Its dominant feature is that reactive trajectories experience the shallow well without entering the deep well region during the course of reaction. The type II mechanism can be further divided into two submechanisms: direct and indirect ones (see the Supplementary Materials). Snapshots of a typical reactive trajectory, which belongs to the cyclic complex direct mechanism, are shown in fig. S6D. Here, the C─H bond is stretched and activated in the cyclic complex configuration region, yielding CD + H products. At 0.01 eV, about 40% of the reactive trajectories follow this direct mechanism, with the indirect mechanism (fig. S6C) that also preferentially forms CD + H accounting for the rest. Reactive trajectories occurring through the type II mechanism lead to a large CD/CH branching ratio of 3.92. In summary, by examining all reactive trajectories at low collision energies, we find that the dynamical effect of the CI-R intermediate elaborated above is quite general, resulting in very large CD/CH branching ratios on the ZMB-b surface. At higher temperatures, trajectories with higher HD rotational excitation are involved, which are less strongly influenced by the CI-induced well. Consequently, this preference is weakened for a thermal population of initial HD(j) states at temperatures in excess of 150 K.
Although there are five electronic states correlating to the reagents C(1D) + HD, our calculations and analysis indicate that the adiabatic dynamics on the lowest two (a∼A′1 and b∼A′′1) is dominant at low collision energies. The three higher excited states can only participate in the reaction via nonadiabatic pathways through CIs and have been neglected in our dynamics calculations. Two types of mechanisms contribute to reaction on the ZMB-b surface. These mechanisms are influenced by the CI-R intermediate, which has large-amplitude C─H stretch and bending vibrational modes (fig. S5 and table S1), diverting the system from the isosceles geometries required for the C2v b∼A′′1-d∼A′′1 CI. Consequently, the reaction system should quickly pass through the C2v CI regions with negligible nonadiabatic transition probabilities. In addition, the MECP on the linear CI seam between the a∼A′1 and c∼A′1 (or b∼A′′1 and d∼A′′1) states is located 12.4 kcal/mol above the reagent asymptote, below which the c∼A′1, d∼A′′1, and e∼A′1 states are not accessible at linear geometries. Furthermore, recent work (30) indicates that the inclusion of Renner-Teller effects is not expected to have a large influence on the results.
Large-scale QD calculations on the ZMB-a and ZMB-b surfaces are also performed to predict detailed scattering properties encoded in differential cross sections (DCSs). Some nonstatistical behavior is observed in the calculated DCSs. Typical three-dimensional product angular distribution plots are presented in fig. S7. More sideways distributions including small peaks are observed, which may be caused by the types I and II mechanisms mentioned above. Meanwhile, interesting oscillation patterns are revealed in fig. S7 (C and D). These arise from quantum interferences between partial waves according to our analysis. This phenomenon has recently been observed experimentally in the H + D2 (32) and H + HD (33) reactions. The oscillation phenomenon in DCSs predicted in fig. S7 is prominent enough to be observed experimentally. However, the types I and II mechanisms do not cause clear bias in the forward or backward directions, and approximately forward-backward symmetric product angular distributions are still obtained.
We also perform extensive ab initio calculations on other similar systems, finding a series of CI-R intermediates. The results of some of our geometry optimization and frequency analyses are given in table S1. In particular, a cyclic CS2 intermediate and the associated CI have been located, with the calculated vibrational frequencies of this cyclic species in excellent agreement with the experimental measurements of Bahou and coworkers (34). In addition, the calculated vibrational frequencies of the CI-R intermediate for PbO2 are also in very good agreement with the experiment, and its corresponding CI is shown to exist in a similar way to the CHD case.
Here, we introduce a general definition of the CI-R intermediate in a bimolecular complex-forming reaction as a special metastable-state intermediate whose conversion to a deep well complex is regulated by a CI-induced barrier. In the title reaction, we find that it has the effect of bond-selective activation, markedly increasing the CD/CH product branching ratios, which are validated by the excellent agreement between theory and experiment. We reveal that the CI-R intermediate leads to two types of reaction mechanisms, having clear nonstatistical features. We have also shown that the CI-R intermediate exists in other systems, and its dynamical effects may have general significance. It is our hope that the CI-R intermediate may become a useful concept in the understanding of unusual phenomena in various complex-forming reactions and in the laser control of chemical reactions.
Experimental measurement
The kinetics of C(1D) + HD reaction were studied experimentally using a continuous supersonic flow reactor over the temperature range of 50 to 296 K using three Laval nozzles based on argon as the carrier gas. Excess concentrations of HD were introduced into the main flow upstream of the Laval nozzle along with CBr4 vapor, which was carried into the reactor by passing a small argon flow over solid CBr4. C(1D) atoms were generated by the pulsed multiphoton dissociation of CBr4 at 266 nm. Previous work (35) has shown that, while ground electronic state C(3P) atoms are the major photolysis product, C(1D) atoms are also created at the 10 to 15% level with respect to C(3P). The C(3P) + HD → CD(CH) + H(D) reaction itself is endothermic by 22.8 kcal/mol, so that this process is negligible in the present work.
The title reaction was investigated by following D atom production. D(2S) atoms were detected through on-resonance vacuum ultraviolet (VUV) laser-induced fluorescence (LIF) using the 1s 2S → 2p 2P0 transition at 121.534 nm. VUV LIF signals from product D(2S) atoms were recorded as a function of time between photolysis and probe lasers. The evolution of the D atom signal (ID) is described by the expressionID=A{exp(−kL(D)t)−exp(−k′t)}(1)k′ = k[HD] + kL(C), where k is the second-order rate coefficient for the C(1D) + HD reaction, [HD] is the HD concentration, and kL(C) is the first-order loss of C(1D) by other processes. kL(D) is the first-order rate coefficient for D(2S) loss, which is dominated by diffusion.
Two types of experiments were performed. The first type of experiment allowed us to determine the temperature-dependent rate coefficients. Here, D(2S) kinetic profiles, such as those shown in fig. S3A, were recorded at different HD concentrations, yielding a range of k′ values. Plots of the individual k′ values versus [HD] allowed the second-order rate coefficient to be determined at a given temperature through linear least squares fits to the data. Typical second-order plots for data recorded at 296 and 50 K are shown in fig. S3B.
The second type of experiment allowed us to derive absolute yields for D(2S) atom production as a function of temperature. Here, the time-dependent relative D atom signal intensity produced by the C(1D) + HD reaction was compared to the one produced by a reference process, namely, the C(1D) + D2 reaction, which is considered to have a 100% D atom yield. A pair of these D atom formation curves recorded at 50 K are shown in fig. S3C. More details of experimental measurements can be found in table S3 and Supplementary Methods.
Ab initio calculations and PESs
Full geometry optimizations were run to locate the MECP of the C2v CI between the b∼A′′1 and d∼A′′1 states and the potential minimum corresponding to the CI-R intermediate for the C(1D) + HD system through ab initio calculations. The internally contracted multireference configuration interaction (36) and five state–averaged complete active space self-consistent field methods (37) were used. Five reference states were used to generate the internally contracted pairs. The active space consists of six electrons distributed among seven orbitals. The basis set used was the Dunning's correlation consistent quadruple-zeta basis augmented by diffuse functions (aug-cc-pVQZ) (38). The corresponding ab initio calculations for other similar systems (CS2, SiO2, etc.) were performed at lower levels. All ab initio calculations were performed with the MOLPRO package (39).
The two highly accurate ab initio global PESs for the a∼A′1 and b∼A′′1 states of the title system constructed by Bian's group were applied; in addition, an adjusted global PES for the b∼A′′1 state, which omits the CI-induced barrier and well, was constructed. The a∼A′1 PES, called ZMB-a, was constructed in our previous work (26), in which the main scheme of PES construction was described. The b∼A′′1 PES constructed by Bian's group was applied in our recent dynamical studies (30) and, for convenience, is referred to as the ZMB-b surface in this work, about which further analysis and more details are given in Supplementary Text and fig. S2. The adjusted b∼A′′1 PES is called the ZMB-bt surface, which is the same as the ZMB-b surface in various regions, except that it does not have the C2v shallow well (one typical contour plot is given in fig. S2D). It is clear that the ZMB-bt surface leaves out the precursor well that supports the CI-R intermediate complex.
QD and QCT calculations
The QD calculations including all Coriolis couplings were performed using the real wave packet approach as implemented in the DIFFREALWAVE code (40). Numerical details are given in Supplementary Methods, and numerous test calculations were performed to check the convergence. Partial wave contributions up to J = 50 and J = 45 were included in the calculations for the a∼A′1 and b∼A′′1 states, yielding converged integral cross sections and DCSs for collision energies up to 0.40 and 0.45 eV, respectively. About 120,000 iteration steps were implemented for each partial wave calculation, which were reduced at high J values.
The QCT calculations were performed using a modified version of the VENUS96 code (41) customized to incorporate the PESs. The QCT method is described in the literature (31), and some computational details are given here. All trajectories were initiated with the reagents separated by 15 bohr. An integration time step of 0.01 fs was chosen, which guarantees an energy conservation of better than 1 in 106. Batches of 10,000 trajectories were calculated for each set of initial conditions with the reagent HD set in different rovibrational states, including those calculated at the temperatures of 50, 75, 127, and 298 K, with the impact parameter randomly sampled between 0 and 14 bohr and with the relative translational energy randomly selected to mimic the Boltzmann distribution at the given temperature.
Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/4/eaaw0446/DC1
Supplementary Methods
Supplementary Text
Fig. S1. Sign changes of the wave function main configuration coefficient for the b∼A′′1 state.
Fig. S2. Contour plots of the ZMB-b and ZMB-bt surfaces.
Fig. S3. Experimental LIF profiles and second-order rate coefficient plots.
Fig. S4. Total reaction probabilities for the C(1D) + HD (v = 0, j = 0) reaction.
Fig. S5. Diagrams of the vibrational modes of the CI-R intermediate in the C(1D) + HD reactive system.
Fig. S6. Internuclear distances and potential energy as a function of time for typical trajectories.
Fig. S7. Three-dimensional product flux plots in the center of mass velocity space for the C(1D) + HD (v = 0, j = 0) reaction.
Table S1. The properties of CI-R intermediates and the CIs associated with them.
Table S2. Comparison between QD and QCT results on the ZMB-a and ZMB-b surfaces.
Table S3. Measured rate coefficients and CD/CH branching ratios for the C(1D) + HD reaction.
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, Monte Carlo sampling for classical trajectory simulations. Adv. Chem. Phys. 105, 171–201 (1999).
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, Direct observation of forward-scattering oscillations in the H+HD→H2+D reaction. Nat. Chem. 10, 653–658 (2018).
M. Bahou,
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, Production and IR absorption of cyclic CS2 in solid Ar. J. Am. Chem. Soc. 122, 661–667 (2000).
R. J. Shannon,
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, The fast C(3P) + CH3OH reaction as an efficient loss process for gas-phase interstellar methanol. RSC Adv. 4, 26342–26353 (2014).
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P. J. Knowles
, An efficient internally contracted multiconfiguration-reference configuration interaction method. J. Chem. Phys. 89, 5803–5814 (1988).
, A second order multiconfiguration SCF procedure with optimum convergence. J. Chem. Phys. 82, 5053–5063 (1985).
T. H. Dunning Jr..
, Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J. Chem. Phys. 90, 1007–1023 (1989).
H.-J. Werner, P. J. Knowles, R. Lindh, F. R. Manby, M. Schütz, P. Celani, T. Korona, G. Rauhut, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, C. Hampel, G. Hetzer, A. W. Lloyd, S. J. McNicholas, W. Meyer, M. E. Mura, A. Nicklass, P. Palmieri, R. Pitzer, U. Schumann, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, Molpro, version 2006.1, a package of ab initio programs (2006); www.molpro.net.
M. Hankel,
S. C. Smith,
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, DIFFREALWAVE: A parallel real wavepacket code for the quantum mechanical calculation of reactive state-to-state differential cross sections in atom plus diatom collisions. Comput. Phys. Commun. 179, 569–578 (2008).
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, Venus96: A general chemical dynamics computer program. QCPE Bull. 16, 671 (1996).
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, Study of the reactions N2++2N2→N4++N2 and O2++2O2→O4++O2 from 20 to 160 K by the CRESU technique. J. Chem. Phys. 80, 4915–4921 (1984).
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, Reaction kinetics to low temperatures. Dicarbon + acetylene, methylacetylene, allene and propene from 77 ≤ T ≤ 296 K. Phys. Chem. Chem. Phys. 10, 729–737 (2008).
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, The reactivity of C(1D) with oxygen bearing molecules NO and O2 at low temperature. Chem. Phys. Lett. 687, 330–335 (2017).
, Kinetic and product study of the reactions of C(1D) with CH4 and C2H6 at low temperature. J. Phys. Chem. A 121, 3851–3857 (2017).
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, An experimental and theoretical investigation of the C(1D) + N2→C(3P) + N2 quenching reaction at low temperature. J. Phys. Chem. A 120, 2504–2513 (2016).
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, Low temperature rate constants for the reactions of O(1D) with N2, O2, and Ar. J. Phys. Chem. A 120, 4838–4844 (2016).
, Low-temperature experimental and theoretical rate constants for the O(1D) + H2 reaction. J. Phys. Chem. A 121, 1916–1923 (2017).
, Quantum mechanical differential and integral cross sections for the C(1D) + H2(v=0, j=0)→CH(v′, j′) + H reaction. J. Chem. Phys. 142, 164309 (2015).
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, Quantum wave packet study of the reaction C(1D) + H2. Chem. Phys. Lett. 480, 46–48 (2009).
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, Infrared spectra of the reaction products of laser ablated lead atoms and oxygen molecules in condensing argon and nitrogen. J. Chem. Phys. 105, 2561–2574 (1996).
Acknowledgments: Funding: This work was supported by the National Natural Science Foundation of China (nos. 21773251, 21473218, and 91741106). J.C. acknowledges the Youth Innovation Promotion Association CAS (no. 2018045). K.M.H. and D.N.-R. acknowledge support from the French program "Physique et Chimie du Milieu Interstellaire" (PCMI) of the CNRS/INSU with the INC/INP cofunded by the CEA and CNES and funding from the "Program National de Planetologie" (PNP) of the CNRS/INSU. W.B. and J.C. acknowledge Beijing National Laboratory for Molecular Sciences and the CAS Key Research Project of Frontier Science. Numerous computations were carried out at National Supercomputing Centers in Shenzhen and Tianjin. Author contributions: W.B. and K.M.H. conceived and supervised the research. K.M.H. and D.N.-R. performed the experiment and analyzed the data. Y.W. and J.C. carried out the QD and QCT calculations and analyzed the data. H.M., C.Z., and Y.W. performed the ab initio calculations. C.Z., H.M., J.C., and W.B. did the work associated with the PESs. W.B., K.M.H., and J.C. wrote the paper with contributions from all co-authors. Competing interests: The authors declare that they have no competing interests. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. Additional data related to this paper may be requested from the authors.
You are going to email the following Conical intersection–regulated intermediates in bimolecular reactions: Insights from C(1D) + HD dynamics
By Yanan Wu, Jianwei Cao, Haitao Ma, Chunfang Zhang, Wensheng Bian, Dianailys Nunez-Reyes, Kevin M. Hickson
Science Advances 26 Apr 2019 : eaaw0446
Unusual metastable-state intermediates are revealed, invoking bond-selective activation via unique reaction mechanisms.

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Pantothenic acid (B-5 & B-6) foods ""
When it comes to optimal energy production, pantothenic acid (B5) and B6 are crucial. Ideally, you must consume those foods that contain them. Even though there is little known about these important vitamins, they are found in a wide variety of foods.
Of this vitamin, very little is known. This vitamin is important for the breaking down of other nutrients for the production of energy.
Pantothenic acid, or vitamin B5, does this by helping in the formation of Coenzyme A, which is essential to many metabolic reactions. It helps the body to synthesize cholesterol to form hormones including testosterone and estrogen.
Shiitake mushrooms are a great supply of vitamin B5. They are low in calories so you should be adding them to your diet in considerable amounts. Beef liver is also an important source, as well as a source of vitamin A. Other animal liver, such as turkey, chicken, and lamb also provide an important amount of this nutrient.
You can also find B5 in avocadoes, milk, yogurt, egg yolk, whole grains, sweet potatoes, and sunflower seeds.
Vitamin B6 is essential to many body functions including metabolism, hemoglobin formation, optimal immune system function, and neurotransmitter formation.
What foods are rich in B6?
Turkey is an important source of this vitamin. Some stores sell cuts of turkey to make it easier for you to add a moderate amount of this food to your diet.
Bananas will complete your daily necessary intake of vitamin B6. Blend frozen slices of banana and other fruits to make a great smoothie.
Chickpeas are one of the most important sources of vitamin B6. This legume is also rich in dietary fiber, folate, thiamin, iron, and plant-based protein.


dubizzle Dubai | Santa Fe: Sport 2.4ltr 4wheel drive.
2015 March Santafe Sport 2.4L. GCC Spec. Bought from Juma Al Majid showroom Diera. All services done by Hyundai Showroom only with service history.Panoramic sunroof, 4wheel drive, Cruise control,Blue tooth with apple play, Covered parking, New tyres nonsmoker used neat and clean car with avg. milage of 9ltr /100kms. No loan, single user.Price negotiable.pls call Show Phone Number.


text:
Andrea Mandorlini (Ravenna, 17 de julho de 1960) é um ex-futebolista e treinador de futebol italiano que atuava como zagueiro ou meio-campista. Atualmente comanda o Padova.

Carreira
Em sua carreira como jogador, iniciada em 1978 no Torino (embora sua estreia oficial fosse em 1979), Mandorlini passou também por Atalanta e Ascoli até 1984, quando foi contratado pela Internazionale, onde viveu sua melhor fase. Destacou-se, principalmente, na temporada 1988-89, onde a equipe treinada por Giovanni Trapattoni obteve a maior pontuação na história da Série A quando as vitórias valiam 2 pontos na época - 58 no total, além de ser um dos líderes de uma defesa que sofreu apenas 19 gols.

Nas temporadas de 1989-90 e 1990-91, perdeu espaço para os jovens Sergio Battistini e Massimo Paganin, embora continuasse importante no elenco nerazzurro e participasse da maioria dos jogos na campanha que deu o título da Copa da UEFA (atual Liga Europa). Depois de 180 jogos e 9 gols, saiu da Inter e assinou com a Udinese, onde permaneceu por 2 temporadas. Chegou a jogar com o argentino Roberto Sensini, um dos principais zagueiros do futebol italiano na década de 1990 e início da década seguinte, antes de se aposentar em 1993, aos 32 anos de idade.

Carreira como técnico
Pouco depois de encerrar a carreira, Mandorlini virou técnico do Manzanese, equipe amadora da província de Údine, porém não teve um bom desempenho. Ainda em 1993, virou auxiliar-técnico do Ravenna, pelo qual deu os primeiros passos no futebol. Voltaria a ser treinador em 1998, comandando a Triestina.

Ele ainda treinou Spezia, Vicenza, Atalanta, Bologna, Padova, Siena, Sassuolo e CFR Cluj (primeiro clube não-italiano em que trabalhou e onde venceu o Campeonato Romeno, a Copa nacional e a Supercopa) até 2010, quando voltaria ao país natal para comandar o Hellas Verona. Em 5 temporadas e meia, levou a equipe da Lega Pro Prima Divisione para a primeira divisão, que não disputava desde 2002, mas terminaria demitido em novembro de 2015 após uma sequência de maus resultados. Desde então, Mandorlini permaneceu o ano de 2016 sem treinar nenhum time. Voltaria à ativa em fevereiro de 2017, substituindo o croata Ivan Jurić no Genoa. Sua passagem pelos Grifoni durou apenas 6 jogos.

Em abril de 2018, foi contratado para o lugar de Attilio Tesser na Cremonese. Foram 15 partidas sob o comando de Mandorlini, com 3 vitórias, 8 empates e 4 derrotas.

Não comandou nenhuma equipe em 2019, voltando à ativa em janeiro do ano seguinte para comandar o Padova pela segunda vez, no lugar de Salvatore Sullo.

Seleção
Mesmo vivendo boa fase na Internazionale, nunca foi convocado para defender a Seleção Italiana principal, tendo jogado apenas 1 vez pela equipe Sub-21, em 1980.

Vida pessoal
Seus filhos, Matteo e Davide, também são jogadores de futebol - o primeiro (nascido em 1988) foi revelado pelo Parma em 2006, atuando em um jogo; Davide (o mais velho, nascido em 1983), assim como seu pai, iniciou a carreira no Ravenna em 2001 e teve passagem razoável pelo Perugia entre 2005 e 2007.

Títulos

Como jogador
Internazionale
 Campeonato Italiano: 1988–89
 Supercopa da Itália: 1989
 Copa da UEFA: 1990–91

Como treinador
Spezia
 Série C2: 1999–00
CFR Cluj
 Campeonato Romeno: 2009–10
 Copa da Romênia: 2009–10
 Supercopa da Romênia: 2010

Naturais de Ravena
Futebolistas da Itália
Treinadores de futebol da Itália
Futebolistas do Torino Football Club
Futebolistas do Football Club Internazionale Milano
Futebolistas da Atalanta Bergamasca Calcio
Futebolistas da Udinese Calcio
Futebolistas do Ascoli Calcio 1898 FC
Treinadores da Società Sportiva Robur Siena
Treinadores do Hellas Verona Football Club
Treinadores da Atalanta BC
Treinadores do Lanerossi Vicenza Virtus
Treinadores do Spezia Calcio
Treinadores do CFR Cluj
Treinadores do Genoa Cricket and Football Club

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Makarieva A.M., Gorshkov V.G., Sheil D., Nobre A.D., Li B.-L.
Remarkably, the effects of condensation/evaporation on air pressure via removal/addition of vapor molecules have managed to escape wide attention for a long time. This to such a degree that, as documented in our paper, there is now a confusion among scientists as to whether condensation increases or reduces moist air pressure. In other words, even the sign of the effect, let alone its magnitude, remains unclear to many meteorologists. This is despite recognition that the lack of theoretical concepts to treat moist effects is a major obstacle for the development of the atmospheric circulation theory (Schneider 2006 p. 682).
In the above paper just made available for public discussion at the Atmospheric Chemistry and Physics Discussions journal of the European Geosciences Union (EGU), we review recent knowledge on the dynamic effects of the phase transitions of water on air circulation and advance the physical foundations of the biotic pump theory in all its integrity. We want the new theory to be scrutinized openly, widely and deeply, and we are ready to invest efforts to clarify and defend our findings in public in the coming weeks. We hope that the EGU platform will be a guarantee that the discussion, including criticisms, will be constructive and of essence.
Please, feel free to join the commentators or to encourage to comment those scientists who you believe might be interested in the topic. The discussion is open until 10 December 2010 during which time the authors will be available to share their insights, for what they are worth, into this really exciting question: Where do winds come from?
hosted by Dr. Judith Curry at Climate Etc.


text:
Q: Command line to install/upgrade .NET Core Are there command line commands to install or upgrade .NET Core?
I checked to see if I had .NET Core was installed on my computer using dotnet --version only to notice that I still had the preview version installed on my computer. I was wondering if I could issue some commands to upgrade it to the latest version.

A: There is no dotnet command to update .Net Core. Instead, you should use the same approach you used to install it in the first place, which depends on your OS.

A: Not promoted officially but it looks like there are approved packages on Chocolatey for .NET Core SDK.
https://chocolatey.org/packages/dotnetcore-sdk
Example:
> choco install dotnetcore-sdk

Or:
> choco upgrade dotnetcore-sdk

Update (December 2020): For .NET 5 the chocolatey package has changed since it's not technically branded as .NET Core any longer.
https://chocolatey.org/packages/dotnet-sdk/
Example:
> choco install dotnet-sdk

Or:
> choco upgrade dotnet-sdk

A: If you have WinGet, then you can use it to install (or update) .NET:
winget install Microsoft.DotNet.SDK.Preview    # currently .NET 7
winget install Microsoft.DotNet.SDK.6
winget install Microsoft.DotNet.SDK.5
winget install Microsoft.DotNet.SDK.3_1

Run from an admin prompt

A: For those who find this on search, there are dotnet-install scripts you can use. For example:
# Windows PowerShell
Invoke-WebRequest -Uri https://dot.net/v1/dotnet-install.ps1 -OutFile "$env:temp/dotnet-install.ps1"; powershell -executionpolicy bypass "$env:temp/dotnet-install.ps1"

# PowerShell Core
Invoke-WebRequest -Uri https://dot.net/v1/dotnet-install.ps1 -OutFile "$env:temp/dotnet-install.ps1"; pwsh "$env:temp/dotnet-install.ps1"

# Shell
wget https://dot.net/v1/dotnet-install.sh && chmod +x ./dotnet-install.sh && sudo ./dotnet-install.sh

* Note the default install location for these is different than the official installers; as said in another answer the easiest path to update is to use the same method you first installed with.
Edit: apt packages for Ubuntu 22.04+ now includes dotnet6 for the SDK. Other dotnet packages, such as just the runtime (dotnet-runtime-6.0, aspnet-runtime-6.0) can be installed as well.
sudo apt update
sudo apt install dotnet6

A: Just a heads up so you (or other people) don't struggle for hours as I did.
.NET Core 1.1.0 ships with SDK 1.0.0 Preview 2 (when this is written), but you need SDK 1.0.0 Preview 3.
Download and install .NET Core 1.1.0 as @svick suggested, then download and install SDK Preview 3 from: https://github.com/dotnet/core/blob/master/release-notes/preview3-download.md

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Do you have left over veggies??
a. Referance the article in the Copper River Record by Judith Lorenz "Dehydration Station"
a. The Senior Center - in Glennallen, Alaska meet the last Thursday of every month at the Senior Center.
THE VEGGIES ARE IN!!! Come get our locally grown vegetables now before our last Farmers Market on September 7th!!
Come to the Glennallen Wednesday Farmers Market to sell or buy local, produce, fresh baked goods as well as local arts and crafts.
Senior Citizen Coupons and WIC accepted.
We're excited to announce we are in the Glennallen Wednesday Farmers Market season is upon us! Come join us every Wednesday from 3pm - 6pm at the Glennallen Chiropractic Center Parking Lot. Join in the fun for the last Wednesday of every month for Kid's Day! Kid's Day events are sponsored by the Glennallen Chiropractic Center Staff, the Child Advocacy Center as well the Kenny Lake 4-H Club!


text:
FlixPatrol TOP 10 iTunes in Bulgaria
TOP 10 on iTunes in Bulgaria on July 29, 2021
All platforms Netflix HBO iTunes
The most popular movies and TV shows on iTunes in Bulgaria. Who was #1 on iTunes on July 29, 2021? TOP 10 charts or full ratings charts. Check the title detail for more streaming analytics.
iTunes TOP 10 in Bulgaria on July 29, 2021
1. n/a Ice Age: Continental Drift
2. n/a RocknRolla
3. n/a Ben-Hur
4. n/a Saw III
5. n/a Patton
6. -3 Monster Hunter
7. n/a Saw
8. n/a Hot Fuzz
9. n/a The Equalizer
10. n/a Frozen II
Top Movies and TV Shows on iTunes in Bulgaria on July 29, 2021 by day


text:
Central Okanagan Area Homes
Kamloops Area Homes
Kelowna Area Homes
Lake Country Areas
North Okanagan Area Homes
Penticton Area Homes
Shuswap Area Homes
South Okanagan Area Homes
Vernon Area Homes
Home Selling Mistakes to Avoid
10 Questions To Ask A Realtor Before Choosing Them To Sell Your House
9-Week Moving Out Checklist To Prepare Yourself for Selling
Ethan St. GermainCanada Flex Realty Group Ltd.346 Lawrence Ave Suite 202 Kelowna, BC V1Y 6L4 M: (250) 299-5278 E: Email Me
How to Ensure Your Home Passes the Home Inspection
By David Harper 1/31/2020
Your House Didn't Sell Now What?
ETHANSTGERMAIN.FLEXREALTYGROUP.CA
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By accessing or using the Site (as defined hereinafter), you are entering into a binding legal agreement with the Company; the website, located at ethanstgermain.FlexRealtyGroup.ca (the "Site"); and the third-party service vendors who use the Site and their parent companies, subsidiaries, and affiliates (the "Company," "us," "we," and "our") relating to terms and conditions of privacy ("Privacy Policy"). This Privacy Policy is in effect for any web page; mobile application; e-mail list; and information, including Personally Identifiable Information, collected/owned by us, regardless of the method of collection, including collection through any online features, services, and/or programs we offer. This Privacy Policy is not applicable to your use of any third-party web page, mobile application, social media site, or any information collected or owned by any entity other than us.
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text:
West Columbia Assistant Police Chief Scott Morrison retires after 26 years
West Columbia Assistant Police Chief Scott Morrison retired after 26 years of service from the WCPD.
The City of West Columbia held a reception last week to congratulate Morrison upon his retirement. The West Columbia City Council also passed a resolution to honor Morrison on June 21. Its contents are posted below.
At the reception, West Columbia Mayor Tem Miles thanked Morrison. Morrison is pictured with WCPD Chief Dennis Tyndall in the feature photo. (City of West Columbia photos.)
Morrison at his reception
"I can't say thank you enough to (Morrison) for the wonderful job he has done for our city," stated Miles. "I extend my heartfelt congratulations to him on his retirement and wish him the very best going forward.
Miles also said Morrison is a great man and he served us well.
Link to Facebook account of retirement
Resolution Recognizing Assistant Police Chief Scott Morrison Upon His Retirement for 26 Years of Service to the City of West Columbia
WHEREAS, Assistant Police Chief Scott Morrison grew up in Irmo, South Carolina and is the son of Larry and
Patricia Morrison. He is married to Laura Privette Morrison and the father of Emily and Hunter Morrison; and
WHEREAS, Assistant Police Chief Scott Morrison graduated from Irmo High School in 1990. In 1994, he
graduated from the University of South Carolina with a Bachelor of Science in Criminal Justice; and
WHEREAS, Assistant Police Chief Scott Morrison began his career with the West Columbia Police Department
on March 20,1995 as a Jailer/Patrol Officer. Throughout his employment with the West Columbia Police
Department, he has also served as Road Sergeant, Training Sergeant, Patrol Lieutenant, Patrol Captain, and
Administrative Captain. He has served as the Assistant Police Chief since 2016; and
WHEREAS, Assistant Police Chief Scott Morrison graduated from the Federal Bureau of Investigations
National Academy (FBINA) in 2012, South Carolina Law Enforcement Coordinating Committee/Law
Enforcement Officers Association Commander School in 2016, and Local Government Leadership Institute in
2020; and
WHEREAS, Assistant Police Chief Scott Morrison has worked as a volunteer with West Columbia's Wellness
Committee, Holy Pursuits Dream Foundation, and the West Columbia Police Officers' Foundation. He is the
founder of the West Columbia Police Officers' Foundation golf tournament and was awarded the West
Columbia Police Department's Jackie Brothers' Integrity Award in 2014; and
WHEREAS, Assistant Police Chief Scott Morrison will retire from the City of West Columbia on June 30, 2021,
after twenty-six years in law enforcement. His entire career has been dedicated to serving the City of West
Columbia and its citizens; and
NOW, THEREFORE, BE IT RESOLVED that the Mayor and City Council of the City of West Columbia does
hereby congratulate and recognize Assistant Police Chief Scott Morrison on his retirement, and honor him for
his twenty-six years of dedicated service to public safety, and the citizens of West Columbia. Assistant Police
Chief Morrison's dedication, professionalism, and leadership will be remembered by this Council, Police
Department, and the employees of West Columbia. City Council wishes Assistant Police Chief Morrison
continued success in his future endeavors.
Tyndall, Morrison, Miles. Former West Columbia Mayor Bobby Horton, background also attended the reception.
Tags: Asst. Chief Scott Morrison, West Columbia Mayor Tem Miles


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What Are Sports Prop Bets?
A proposition bet in sports betting are more commonly known as a "prop bet." This kind of betting is very popular overseas. It is now one of the fastest growing segments of the sports betting industry in the United States. The growth of prop betting in Nevada sportsbooks is evolving and constantly changing as gaming control boards open up to the new kinds of opportunities.
Some prop bets may sometimes appear to be similar to futures bets. The difference between the two bets is that a prop bet is a wager on an individual player or specific event. However, the majority of prop bets at a sportsbook are on individual players and not the entire team during a game. Both opportunities may be available depending on the game.
For example, Super Bowl 53 touchdown props:
Prop bets became popular in the United States with the Super Bowl. The specific explosion of prop betting started at the Westgate in Las Vegas (previously known as Las Vegas Hilton). The team at the Las Vegas SuperBook was the first Nevada sportsbook operator to offer a large number of prop bets for an individual game. Today, all sportsbook operators in Nevada today offer hundreds of Super Bowl prop bets, and new online sportsbook operators in New Jersey (like DraftKings Sportsbook pictured above) are expected to follow with a huge offering of props in 2019.
Prop betting started modestly with the Super Bowl but continues to grow. Some sportsbook operators offer prop bets every week during the pro football season. Fewer sportsbook operators offer prop bets every day for other sports. The evolution of prop betting in United States sportsbooks is taking the wagers off the field.
Modern prop bets
Prop bets in Nevada may be available for non-game events such as award winners (i.e. Mike Trout to win AL MVP), major league drafts (i.e. NFL draft), and even simple yes or no bets on teams to do something (i.e. Will the New York Jets make the playoffs).
Sportsbook operator William Hill even allows customers to email or tweet suggestions for an individual prop bet. As long as the bet proposition works within the Nevada Gaming Control Board guidelines William Hill will add them to their mobile sports wagering app menu.
Prop bets may be the most exciting kind of wagering opportunities the United States right now. Offshore sportsbook operators offer prop bets on everything from who will be president to the number of yards a wide receiver might have. That's not the case in the United States.
Even though the growth of prop bets seems limitless, gaming regulators have limits that keep prop bets in sportsbooks limited to, well, sports. Additionally, all prop bets must be reconcilable through information and data from the sport being wagered on. Even awards in sports must be reconcilable by official league information.
Having said that, sportsbook operators have a good amount of freedom within gaming control board parameters. If a player is on a hot streak, a sportsbook operator may choose to make short-term prop bets available. Since the information is tabulated on the field, these are quickly made available.
Coin Toss Props at DraftKings Sportsbook
Exotic prop bets
Exotic prop bets are only offered by some sportsbooks around the world. These non-traditional prop bets are not necessarily based on activities that take place during a game. The most popular of these exotic prop bets, such as the length of the national anthem or the coin toss results, happen during the Super Bowl.
These props can be as outlandish as the sportsbook operator wants them to be. They usually take place during the most publicly popular events such as a Royal Wedding in the United Kingdom or who will play a specific role in a movie series.
While they may be fun, these kind exotic proposition bets are not legal in America. The Nevada Gaming Control Board has not seen these wagers fit for approval yet. This could change in Nevada and in other states that may legalize sports betting in America.
Personal prop bets
Proposition betting doesn't only take place in a sportsbook. Bets with a friend for random activities also fall into the category of a prop bet. For example, a bet that a friend can't finish 40 pushups during a game of poker might be considered a personal prop bet between friends.


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Samimy, Mo
Mo Samimy
Emeritus, Mechanical and Aerospace Engineering
samimy.1@osu.edu
Dr. Mo Samimy is the John B. Nordholt Professor of Mechanical and Aerospace Engineering and the founder of the Aerospace Research Center at The Ohio State University. Dr. Samimy has educated a large number of engineers and scientists who are currently in academia, national laboratories, and industry. He has served on various national committees and editorial boards and has lectured extensively in the U.S. and abroad. He is a fellow of four major national societies: the American Institute of Aeronautics and Astronautics (AIAA), the American Society of Mechanical Engineers (ASME), the American Physical Society (APS), and the American Association for Advancement of Science (AAAS). His research interests are in flow physics and control and jet aeroacoustics. He has published over 300 technical papers on these topics. He has received numerous awards, including, the College of Engineering Clara and Peter Scott Faculty Award for Excellence in Engineering Education, Alumni Distinguished Graduate Faculty Award for Student Mentoring, and OSU's Distinguished Scholar Award. The University Distinguished Scholar Award, one of the highest awards within the university, recognizes and honors six faculty members each year, from all the fields and from over two thousand faculty, who have demonstrated scholarly activity, research, or other creative works which represent exceptional achievements in their fields.
Turbulence, compressible flows, aeroacoustics, experimental techniques, flow control


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Gators-North Carolina NCAA baseball tournament game to resume at 5:45 p.m.
Garry Smits
GAINESVILLE | A thunderstorm has delayed play for a second day in a row for the Florida Gators in the NCAA regional baseball tournament at McKethan Stadium.
After teams were pulled off the field by umpires at about 2:30 p.m., officials planned to resume UF's elimination game against North Carolina game at 5:45 p.m., with the Tar Heels batting in the bottom of the third. There are two runners on and none out in the scoreless game.
UF's opening game against the College of Charleston was delayed for more than three hours on Friday. The top-seeded Gators lost to No. 4 Charleston 3-2 with the game concluding at 1:15 a.m. Saturday.
Florida has been unable to mount an offense so far in the tournament, despite pitching well. After Charleston scored all of its runs in the first inning, three Gator pitchers, Tyler Shore, Justin Shafer and second-game starter Bobby Poyner have combined to pitch 10 scoreless innings. Shafer retired all 12 batters he faced against the Cougars, with five strikeouts.
UF has 10 hits in 11 innings but has left the bases loaded three times without scoring and has stranded 17 runners.
North Carolina lost its MVP, junior shortstop Michael Russell, when he was beaned by Poyner in the second inning. Russell was bleeding profusely from the area around his left ear and under NCAA rules, the Tar Heels medical staff was given 10 minutes to attempt to stop the bleeding.
However, Russell was unable to return. He leads Carolina in average (.344), runs scored (43), hits (77), doubles (20), home runs (four), RBI (32) and stolen bases (13). There was no immediate word on whether he could play on Sunday if the Tar Heels beat Florida.
The Florida-North Carolina winner advances to a 1 p.m. game on Sunday against the loser of Saturday's winner's bracket final between Charleston and Long Beach State.
The winner of that game will take on the Charleston-Long Beach winner at 7 p.m. on Sunday. If the unbeaten team loses, a final game will be needed Monday at 7 p.m.
Garry Smits: (904) 359-4362


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Mars 2020's Final Four
This Mars map depicts the final four locations under consideration for the landing site of Mars 2020. The topographic map of Mars was created by the Mars Orbital Laser Altimeter (MOLA) on board the robot Mars Global Surveyor spacecraft. MOLA measured heights on Mars by precisely determining the time it took for a low power laser beam to bounce off the surface.
NASA/MGS/MOLA Science Team
Original (12,032 x 6,912)
[51, 175, 180]
Vaneeza Rupani (inset), a junior at Tuscaloosa County High School in Northport, Alabama, came up with the name Ingenuity for NASA's Mars Helicopter (an artist's impression of which is seen here) an...
High School Junior Names NASA's Mars Helicopter
Andrea Connell, software engineer at NASA's Jet Propulsion Laboratory in Southern California, works with the Component-based Campaign Planning, Implementation, and Tactical software tool, or COCPIT...
Perseverance Mars Rover's COCPIT Program
Missions to outer space have come a long way since the days of Cold War competition. Farah Alibay finds that building relationships is a big part of building spacecraft.
This series of images shows the Martian moon Phobos as it crossed in front of the Sun, as seen by NASA's Curiosity Mars rover on Tuesday, March 26, 2019 (Sol 2359).
Curiosity Observes Phobos Eclipse: Sol 2359
NASA Mars Helicopter team members work the flight model (the vehicle going to Mars) in the Space Simulator.
Working Mars Helicopter
This stereo view from the Navigation Camera (Navcam) on NASA's Curiosity Mars rover shows a 360-degree panorama around the location where the rover spent its 1,000th Martian day, or sol, on Mars. T...
Panorama from Curiosity's Sol 1000 Location (Stereo)
This composite image, made from four taken by the SuperCam instrument aboard NASA's Perseverance rover on Aug. 8, 2021, shows the hole in a Martian rock where the rover attempted to collect its fir...
Laser Shots at 'Roubion'
Scientists use the color swatches on the primary calibration target for Mastcam-Z – a pair of zoomable cameras aboard NASA's Perseverance Mars rover – to fine-tune the cameras' settings. Symbols an...
Mastcam-Z's Calibration Target
This image, taken in the Spacecraft Assembly Facility's High Bay 1 at the Jet Propulsion Laboratory in Pasadena, California, on July 23, 2019, shows a close-up of the head of Mars 2020's remote sen...
The Tippy Top of Mars 2020
A slice of a meteorite scientists have determined came from Mars placed inside an oxygen plasma cleaner, which removes organics from the outside of surfaces. This slice will likely be used here on ...
Cleaning a Martian Meteorite
Cumulative driving by NASA's Mars Exploration Rover Opportunity surpassed marathon distance on March 24, 2015, as the rover neared a destination called "Marathon Valley," which is middle ground of ...
Opportunity's Approach to 'Marathon Valley' (Stereo)
This recording was made on Feb. 22, 2021, on the fourth sol (Martian day) by the SuperCam instrument on NASA's Perseverance rover after deployment of the rover's mast.
Perseverance Rover's SuperCam Records Wind on Mars
When the NASA Perseverance Mars rover lands on the Red Planet, it will be caching rock samples for a future mission to collect and return to Earth. For Mars 2020 Deputy Project Scientist at NASA-JP...
Seeking Signs of Life in Ancient Martian Rocks
Mastcam-Z, a pair of zoomable cameras aboard NASA's Perseverance rover, imaged its calibration targets for the first time on Feb. 20, 2021, the second Martian day, or sol, of Perseverance's mission...
Mastcam-Z Looks at Its Calibration Target
NASA's Perseverance rover has been on the surface of Mars since February of 2021, joining NASA's Curiosity rover, which has been studying the Red Planet since 2012.
Mars Report: Update on NASA's Perseverance Rover & Curiosity Rover (May 20, 2021)
The photo was taken on March 16, 2020 in a cleanroom at NASA's Kennedy Space Center during final preparation for launch.
Rover Evolution Plate Getting Ready for Mars
This kickoff of a new Mars video series covers Opportunity's 14th anniversary on the Red Planet, Curiosity's spectacular panorama and ice deposits spotted by an orbiter.
Mars Report: January 2018
The Return to Earth camera on NASA's Ingenuity Mars Helicopter snaped this picture of geologic feature the Mars Perseverance rover team calls "Raised Ridges" during its 10th flight at Mars, on July...
Aerial View of Jezero Crater's 'Raised' Ridges
Can we fly on Mars? The laws of physics may say it's near impossible, but actually flying a heavier-than-air vehicle on the Red Planet is much harder than that. NASA's Mars 2020 mission will del...
NASA Chopper Ready for a Spin on Mars
This image from NASA's Perseverance rover shows the agency's Ingenuity Mars Helicopter right after it successfully completed a high-speed spin-up test. It was captured by the Mastcam-Z instrument o...
Ingenuity Right After a Spin
This artist's concept is loosely based on the Curiosity rover in NASA's Mars Science Laboratory mission. Mission planners would potentially leverage aspects of this rover design for a Mars mission ...
Mars Rover Artist's Concept
An electrical cable can be seen snaking its way along insulation material in this in-flight image of the interior of the Mars 2020 spacecraft on its way to the Red Planet. The picture was assembled...
Mars 2020 Showing Some Inflight Heat
The HiRISE camera aboard NASA's Mars Reconnaissance Orbiter was able to capture this image of the final location of the heat shield that helped protect NASA's Perseverance rover during its landing ...
Close-Up of Perseverance Heat Shield on the Martian Surface
This artist's concept depicts astronauts and human habitats on Mars. NASA's Mars 2020 rover will carry a number of technologies that could make Mars safer and easier to explore for humans.
First Humans on Mars