text:
\section{Introduction}
Nanoalloys comprising two or more metal atoms within a finite framework offer novel physical and chemical properties significantly different from their bulk alloy counterparts\cite{nanoalloys}. The sensitivity of their properties to system size and composition gives ample room for fine tuning as desired for various applications in catalysis, optics and electronics\cite{Johnstonbook}. Understanding the effects of size, structure, composition, chemical ordering and temperature on the emergent behaviour of nanoalloys thus plays a key role in their fabrication and functional optimization.

Although a lot of scientific literature within current nanoscience addresses the role of ground state nanoalloy configurations on the observed properties\cite{nanoalloys,Johnstonbook, nanoalloy_book, FerForJohn}, effects at finite-temperature have received less attention\cite{calvo_nanoalloy,polak}. One such property is the solid-liquid-like phase transition temperature which has already been found, both experimentally\cite{jesser1,jesser2} and in theoretical simulations\cite{th1,th2,th3,th4}, to depend on the size and composition of nanoalloys. Moreover, the phase transition behaviour changes qualitatively as well; different melting stages (premelting) were observed in Cu-Au system\cite{lopez} in contrast to Ag-Au bimetallic clusters\cite{silvergold} which showed a single stage melting. Complex structural transformations, including switching among homotops before complete melting, have also been observed\cite{struc1,struc2}.

Compositional dependence of the phase transition temperature in alloys is studied through the construction of phase diagrams. Extension of the phase diagram to nanoscale materials for predicting the solid-liquid-like phase transition temperature has been already attempted\cite{th1,pd2,pd3,pd4}. Models typically used for bulk phases\cite{bulk1,bulk2} are unsuitable for these systems and hence, sensitive first-principles treatment of the electronic structure is necessary. In our previous study\cite{self}, we showed that density functional theory (DFT) was able to capture the solid-liquid-like phase transition temperature of Ga\textsubscript{19}Al\textsuperscript{+} in excellent agreement with experiments\cite{jarroldGa19Al}. In this work, we explore two more cluster sizes in the Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} cluster series: Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}, and attempt to create a phase diagram of Ga-Al nanoalloy system using the phase transition temperature data of monometallic phases, Ga\textsubscript{20}\textsuperscript{+} and Al\textsubscript{20}\textsuperscript{+} respectively\cite{krista1,selfAl}.

Cationic gallium clusters have been observed to show melting-like transition at temperatures significantly above the bulk melting temperature of gallium\cite{jarrold_secondorder, jarrold_PRB, jarrold_GaJACS, jarrold_GaPRL,Krista_PRB}. However, a recent study by Jarrold and co-workers\cite{Jarrold60} have found the  gallium cluster comprising 95 atoms to be the first cluster in the size range 60-183 atoms to melt below the bulk melting temperature. Although not observed in experiments due to limitations on the temperature range\cite{Al16-48}, greater-than-bulk melting behaviour has also been predicted for aluminium clusters\cite{selfAl}. An aluminium atom, being isoelectronic and having a similar ionization potential (IP), has a vacant \textit{d}-shell and is 5.4\% smaller in atomic radius in comparison to a Ga atom. Moreover, the overlap of valence \textit{s} and \textit{p} orbitals is different for both the metals since the \textit{4s} band of Ga is shifted to a higher binding energy in comparison to the \textit{3s} band of Al\cite{Eberhardt}. These differences raise the question as to how the thermodynamics of Ga-Al clusters change with composition in the nano-regime, and also how is it different from the corresponding bulk Ga-Al alloy system. The aim of this report is to answer the above question and also to understand further the differences between the behaviour of the internal and surface atoms of the cluster and how they affect the phase transition, as has been observed in Ga\textsubscript{20}\textsuperscript{+} and Al\textsubscript{20}\textsuperscript{+} clusters\cite{selfAl}. The organisation of the work is as follows: section 2 describes the computational method adopted for this study. In section 3 we present the results obtained using various statistical tools and indices to explain the spatial and temporal variations occurring during the phase transition of Ga$_{11}$Al$_{9}^+$ and Ga$_{3}$Al$_{17}^+$ clusters and go on to complete the phase diagram of the 20-atom Ga-Al system. Finally we summarise and conclude in section 4.

\section{Computational details}
We adopted a similar methodology for studying the melting transitions in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} clusters as has been described in our previous works\cite{self, selfAl}. Density functional theory (DFT) calculations were performed using the plane waves basis set based code Vienna \textit{ab-initio} simulation package (VASP)\cite{vasp1,vasp2,vasp3,vasp4}. Large core (i.e. only \textit{3s$\rm^{2}$3p$\rm^{1}$} and \textit{4s$\rm^{2}$4p$\rm^{1}$} electrons were considered as valence for Al and Ga respectively) projector-augmented wave (PAW)\cite{paw1,paw2} pseudo-potentials in combination with the generalized gradient approximation in the Perdew-Wang form (GGA-PW91)\cite{PW91a,PW91b} were used. The starting structures for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}  clusters (as shown in Fig.~\ref{structure}) were determined using the stacked plane (SP)\cite{krista1,self} Ga$_{20}$ structure. Each of the 20 available sites in the SP configuration of Ga$_{20}$ was substituted by a single Al atom and based on the calculated free energy of the cluster, the sites were numbered in ascending order. The first nine and seventeen sites served as the positions for Al atoms in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} respectively.

Born-Oppenheimer molecular dynamics (BOMD) as implemented in VASP in addition to parallel tempering (PT) was used to perform the molecular dynamics simulations in the microcanonical ensemble. 19 different temperatures between 250 K and 1150 K at 50 K intervals were chosen to capture the solid-liquid-like phase transition. Relative convergences of the canonical and microcanonical specific heat curves obtained using the multiple histogram (MH) method\cite{CalvoPTMD, krista1}, ascertained using the sliding window analysis\cite{krista1}, were achieved after a total run time of 160 ps (step size 2 fs) for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and 46.2 ps (step size 0.8 fs) for Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}. A smaller step size was used in Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} to counter the increase in energy during microcanonical runs. Parallel tempering (PT) helps to avoid the dependence of thermodynamics on the starting structure and the  possibility of the structure getting trapped in one of the local minimas in the potential energy surfaces of Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}. After every 100 time steps, each of the 19 different microcanonical runs was stopped. Two configurations were randomly selected and based on the calculated acceptance probability\cite{Calvo_PTMD_new}, swapping was either accepted or rejected. The spatial charge distribution analysis was performed using freely available software\cite{henkelman} based on the quantum theory of atoms-in-molecules (QTAIM)\cite{bader}.

\section{Results and Discussion}

\subsection{Phase transition in Ga$_{11}$Al$_{9}^+$ and Ga$_{3}$Al$_{17}^+$}
The top panel of Fig.~\ref{spheat} shows the canonical heat capacity curves obtained from the MH method for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} clusters normalized to the classical specific heat capacity ($C_{0} = (3N - 6 + 3/2)k_{B}$ where N is the number of atoms and $k_{B}$ is the Boltzmann constant) accounting for rotational and vibrational contributions. The solid-liquid-like phase transition temperature, corresponding to the peak in canonical specific heat capacity plot, is 824 K for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and 922 K for Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} cluster respectively.

Analyses of the indices pertaining to the cluster structure at different temperatures help to relate the structural changes occurring in the cluster to its thermodynamic behaviour. Melting, in the context of clusters, is a change from the \textit{solid-like} state to the \textit{liquid-like} state. The root mean squared (RMS) bond-length fluctuation (Berry parameter\cite{Berry_parameter}) identifies this phase transition i.e. the melting-like temperature as the temperature above which the average change in bond-lengths converge. Expressed as $\delta_{rms}$,

\begin{equation}
\delta_{rms} = \frac{2}{N\cdot(N-1)}\sum_{i>j}\frac{(<r_{ij}^{2}>_{t} - <r_{ij}>_{t}^{2})^{1/2}}{<r_{ij}>_{t}}
\end{equation}
\\
where N is the total number of atoms, $r_{ij}$ is distance between atoms i and j and $<>_{t}$ denotes the time average, this index of fluctuation quantifies the response of bond vibrations to increasing energy (or temperature).

Shown in the bottom panel of Fig.~\ref{spheat} are the calculated $\delta_{rms}$ values for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} (shown in blue) and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} (shown in red) clusters. The fluctuations in bond-length are quite low $(\sim 0.1- 0.15)$ at the lowest energy and start to increase with temperature. However, above the calculated solid-liquid-like phase transition temperature of 824 K in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and 922 K in Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}, the values converge to $(\sim 0.3)$ indicating a structural transition. It must, however, be stated that although at low and high temperatures the values of $\delta_{rms}$ are consistent with PT independent simulations, the absolute value of the index in the intermediate temperature range is subject to the influence of PT.

\begin{figure}[t]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true,width=\columnwidth]{SpheatLind.eps}
\caption{Comparison of canonical specific heat curves of Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} (top panel) and the root-mean-squared (RMS) bond-length fluctuations (bottom panel) as a function of temperature.}
\label{spheat}
\end{figure}

Mean squared displacement (MSD) helps to compare the relative mobilities of the internal and surface atoms. Calculated as per Eq.~\ref{msd},
\begin{equation}
<r_{i}(t)> = \frac{1}{M}\sum_{m=1}^{M}[R_{i}(t_{m}+t) - R_{i}(t_{m})]^{2}
\label{msd}
\end{equation}
where M is the number of time origins, the individual atomic contributions to the overall behavior of the system can be analyzed. Fig.~\ref{msdGa11Al9} shows the MSD of gallium and aluminium atoms of Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} at the lowest and highest energy. Coloured in indigo, the amplitude of the MSD of the surface gallium atoms (averaged) does not change significantly as the energy is increased. Al atoms present at the internal sites (red and blue) show the maximum increase in the amplitude of MSD from lowest to the highest energy. Moreover, at the highest energy all the Al atoms have almost similar MSDs indicating a \textit{liquid-like} phase.
\begin{figure}[t!]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true, width=\columnwidth]{msd_Ga11Al9.eps}
\caption{Comparison of mean squared displacement (MSD) of Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} at lowest (246 K) and highest energy (931 K) as a function of time. Atoms in red and blue are the central Al atoms; green and orange corresponds to MSD averaged over all the Al atoms in the central and top ring respectively; indigo represents the average MSD of Ga atoms as also shown in inset. For references in the text, the more highly coordinated internal atom (red) is referred as \textit{a} and the other (coloured blue) as \textit{b}.}
\label{msdGa11Al9}
\end{figure}

\begin{figure}[t!]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true, width=\columnwidth]{msd_Ga3Al17.eps}
\caption{Comparison of mean squared displacement (MSD) of Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} at lowest (286 K) and highest energy (1079 K) as a function of time. Atoms in red and blue are the central Al atoms; turquoise and indigo corresponds to MSD averaged over all the surface Al and bottom ring Ga atoms respectively. Orange represents the MSD of top Ga atom. For references in the text, the more highly coordinated internal atom (red) is referred as \textit{a} and the other (coloured blue) as \textit{b}.}
\label{msdGa3Al17}
\end{figure}
Fig.~\ref{msdGa3Al17} shows the MSD calculated for Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} at the lowest and highest energy. In contrast to the Ga atoms in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} (average MSD of all Ga atoms coloured indigo in Fig.~\ref{msdGa11Al9}) where the MSD have similar amplitudes for all the atoms at the lowest and highest energies, one of the three Ga atoms situated at the top (colored orange in inset) has MSD values between those of internal atoms and other surface atoms. This difference, however, vanishes as the energy is increased and all the surface atoms have similar MSD values. It is for the internal Al atoms (red and blue) that the MSD changes with increasing temperature. At the highest energy, all the atoms (Ga and Al) have MSD values reflecting a \textit{liquid-like} state in Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}.

The diffusion coefficient helps to quantify the mobility of atoms in the cluster. It is calculated as per Eq.~\ref{diffcoeff} where D is the diffusion coefficient of the specific atom, $<r_{i}(t)>$ is the mean squared displacement of the corresponding atom calculated as per Eq.~\ref{msd} and d is the dimensionality of the cluster system (which is 3). For small systems such as clusters, the diffusion coefficient is meaningful only over a small time range where the MSD achieves a constant slope\cite{berry_msd}.
\begin{equation}
D \equiv \frac{1}{2d}\lim_{t\rightarrow\infty}\frac{<r_{i}(t)>}{t}
\label{diffcoeff}
\end{equation}

\begin{figure}[t]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true, width=\columnwidth]{DC.eps}
\caption{Diffusion coefficient of internal and surface atoms as a function of temperature. The vertical dotted line denotes the melting temperature.}
\label{DC}
\end{figure}

Shown in Fig.~\ref{DC} are diffusion coefficient values calculated for Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} clusters in the top and bottom panels respectively. The MSD values over which the slope is calculated have been kept fixed between 1 and 2 \AA$^2$. MSD values of all the surface gallium and aluminium atoms have been averaged as shown in black and green for both the clusters. In both cases, the diffusion coefficients of the surface atoms are very high with the trend increasing with temperature. The average coordination number, calculated using the first minimum in pair distribution function $g(r)$ as cutoff distance for coordination, of Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} (Fig.~1, Supplementary Information) shows that the internal atoms (red and blue) occupy an internal site at all temperatures below the melting temperature of 824 K. In the top panel of Fig.~\ref{DC}, the diffusion coefficient of both the internal atoms is much lower at all temperatures up to 701 K after which the internal atom \textit{a} (coloured red in inset of bottom panel, Fig.~\ref{msdGa11Al9}) shows fluctuations in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+}. However, it is only after the melting temperature that the diffusion coefficient of the internal atoms shoots up and at the highest average temperature becomes comparable with the rest of the Al atoms in the Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} cluster.

Although the surface Ga and Al atoms of Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} show similar behaviour with increasing temperature,  constant exchange among atoms to occupy an internal site at temperatures closer to the melting temperature (as also clear from the average coordination number plot in Fig.~2, Supplementary Information) makes it much harder to tag a particular atom as \textit{internal}. To counter this situation, we attribute the term `\textit{persistent internal}' to an atom which satisfies the following two conditions: (a) the average coordination number has to be greater-than-or-equal-to 9.5 and, (b) the time during which condition (a) is satisfied during the continuous MD run has to be more than 1.5 ps. The second condition also helps to make sure that an atom occupying an internal site at a particular energy run is favourable rather than being an artefact of parallel tempering.

Coloured orange in the top and bottom panels of Fig.~\ref{DC}, the diffusion coefficient of the `\textit{persistent internal}' atom(s) in both the clusters is much lower in comparison to the surface atoms below the melting temperature. Above the melting temperature, none of the atoms in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} satisfy the condition to be considered as `\textit{persistent internal}'. In Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}, in contrast, the `\textit{persistent internal}' atom criteria is fulfilled up to 967 K, above the melting temperature of 922 K. Moreover, in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} the diffusion coefficient of the `\textit{persistent internal}' atom is an average of both the internal atoms (red and blue) up to 582 K.

The Quantum Theory of Atoms in Molecules (QTAIM)\cite{bader} aims to define atomic boundaries within a molecule using the topology of the total electronic charge density of the molecular system. The volume occupied by an atom, which is an open system, is governed by the topological condition of zero-flux of the electronic charge density ($\bigtriangledown \rho ( r )\cdot n ( r ) = 0$). Integrating the electron density within each atomic volume gives the total electronic charge associated with the corresponding ion.

\begin{figure}[t]
\centering
\subfigure[Ga$_{20}^{+}$]{\includegraphics[trim = 1.7cm 1cm 1.7cm 0cm,clip=true,width=0.325\columnwidth]{Ga20+.eps}}
\subfigure[Ga\textsubscript{19}Al\textsuperscript{+}]{\includegraphics[trim = 1.7cm 1cm 1.7cm 0cm,clip=true,width=0.325\columnwidth]{Ga19Al+.eps}}
\subfigure[Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+}]{\includegraphics[trim = 1.7cm 1cm 1.7cm 0cm,clip=true,width=0.325\columnwidth]{Ga11Al9+.eps}}
\subfigure[Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}]{\includegraphics[trim = 1.7cm 1cm 1.7cm 0cm,clip=true,width=0.325\columnwidth]{Ga3Al17+.eps}}
\subfigure[Al\textsubscript{20}\textsuperscript{+}]{\includegraphics[trim = 1.7cm 1cm 1.7cm 0cm,clip=true,width=0.325\columnwidth]{Al20+.eps}}
\caption{ Starting structures in the capped sphere (Ga$_{20}^{+}$) and stacked plane (Ga\textsubscript{19}Al\textsuperscript{+}, Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+}, Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} and Al\textsubscript{20}\textsuperscript{+}) configurations with Al atoms in white and Ga atoms in cyan.}
\label{structure}
\end{figure}

Shown in Fig.~3 (Supplementary Information) are the partial charges associated with each of the gallium and aluminium atoms in Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} respectively. There is a strong charge segregation between the internal and surface atoms in both the cases. Moreover, among the charged surface atoms it is the gallium atom which becomes negatively charged and aluminium which becomes positively charged in both cases. A similar picture, where an electrostatic cage confines the internal atoms was also observed for the monometallic Ga\textsubscript{20}\textsuperscript{+} and Al\textsubscript{20}\textsuperscript{+} clusters\cite{selfAl}.
\subsection{Phase diagram of Ga-Al}

Incorporating the results from our previous investigations\cite{self,selfAl} of Ga\textsubscript{20}\textsuperscript{+}, Al\textsubscript{20}\textsuperscript{+} and Ga\textsubscript{19}Al\textsuperscript{+}, we have created a binary phase diagram of the 20 atom Ga-Al nanocluster system. Irrespective of the bimetallic cluster's composition, the solid-liquid-like phase transition temperature is always above the corresponding bulk alloy melting temperature\cite{bulkGaAl} as also shown in Table~\ref{melttemp}.

\begin{table}[b]
\centering
\caption{Comparison of the melting temperatures of Ga-Al alloys in cluster and bulk phase\cite{bulkGaAl}.}
\begin{tabular}{c c c c}
\hline
\hline
 & Cluster T$_{m}$(K) & Bulk T$_{m}$(K) & $\Delta T_m$(K) \\
 \hline
Ga$_{20}^{+}$ & 616 & 303 & 313 \\
Ga\textsubscript{19}Al\textsuperscript{+} & 686 & 353 & 333 \\
Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} & 824 & 646 & 178 \\
Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} &  922 & 857 & 65 \\
Al\textsubscript{20}\textsuperscript{+} & 993 & 933 & 60 \\
\hline
\end{tabular}
\label{melttemp}
\end{table}

\begin{figure}[t!]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true,width=\columnwidth]{Mixing_Bader.eps}
\caption{Excess energy for all the compositions in Ga$_{20-x}$Al$_{x}$$^+$, panel (a), and the corresponding atoms-in-molecules analysis where the red dot, blue open circle and turquoise circle represents negative, neutral and positive charges.}
\label{mixingenergy}
\end{figure}

The energy of mixing, calculated as per Eq.~\ref{excessenergy}, reflects the energy gain (or loss) for a mixed cluster relative to the pure clusters. A negative value indicates mixing i.e. formation of the nanoalloy is energetically favourable, whereas a positive value indicates segregation between the participating atoms.

\begin{equation}
E_{exc} = E_{tot}^{Ga_{(20-x)}Al_{x}^{+}} - \frac{x}{20}E_{tot}^{Al_{20}^{+}} - \frac{20-x}{20}E_{tot}^{Ga_{20}^{+}}
\label{excessenergy}
\end{equation}
Fig.~\ref{mixingenergy}~(a) shows the energy of mixing for all the cluster compositions in the series Ga$_{(20-x)}$Al$_{x}$$^+$. Adding an aluminium atom to Ga$_{20}^{+}$ gives a positive value to the energy of mixing indicating segregation of the Al atom in the gallium dominated Ga\textsubscript{19}Al\textsuperscript{+} cluster. The energy of mixing remains positive for Ga$_{18}$Al$_{2}$$^+$ and from Ga$_{17}$Al$_{3}$$^+$ onwards it becomes negative, achieving a minimum at the most favourable composition, i.e. Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+}. This trend is also visible from the change in melting temperature between the Ga$_{(20-x)}$Al$_{x}$$^+$ clusters and the corresponding bulk alloy counterparts as shown in Table\ref{melttemp}. The change in melting temperature first increases from Ga\textsubscript{20}\textsuperscript{+} to Ga\textsubscript{19}Al\textsuperscript{+} but thereafter decreases with increasing Al composition thus reflecting how the energy of mixing affects the greater-than-bulk melting behaviour of Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} clusters.

In order to understand further how the charge distribution among atoms, i.e. with respect to internal \& external sites, affects the segregation or mixing behaviour in each cluster composition in Ga$_{(20-x)}$Al$_{x}$$^+$, we performed atoms-in-molecules analysis as shown in panel (b) and (c) of Fig.~\ref{mixingenergy}. The optimized structure for each of the nanoalloy clusters was obtained from the SP configuration of Ga$_{20}$ as has been explained in Section 2. From the obtained partial charges on each atom ($q_i$), an atom is considered neutral if $-0.1e \le q_{i} \le 0.1e$, positively charged if $q_{i} > 0.1e$ and negatively charged if $q_{i} < -0.1e$. The Ga$_{20}^{+}$ capped sphere structure\cite{krista1} has one internal negatively charged atom and one positively charged surface atom with the remaining atoms being neutral. In Ga\textsubscript{19}Al\textsuperscript{+}, the internal Al and Ga atom becomes strongly positively and negatively charged respectively, thus forming a dipole with no negatively charged surface atoms. In Ga$_{18}$Al$_2$$^+$ and Ga$_{17}$Al$_3$$^+$, both the internal atoms are positively charged. However, for Ga$_{17}$Al$_3$$^+$, there is a negative charge on the surface. Starting from Ga$_{16}$Al$_4$$^+$, there is one neutral Al atom occupying the internal site with the other being positively charged until Ga$_{14}$Al$_6$$^+$ and negatively charged from Ga$_{13}$Al$_7$$^+$ to Ga$_{17}$Al$_3$$^+$. Both the internal atoms are negatively charged for Ga$_{2}$Al$_{18}$$^+$, GaAl$_{19}$$^+$ and Al\textsubscript{20}\textsuperscript{+}. Correlating with the energy of mixing, as shown in Fig.~\ref{mixingenergy}(a), we see that segregation (a positive energy of mixing) corresponds to either the formation of a strong dipole between the internal atoms (as in Ga\textsubscript{19}Al\textsuperscript{+}) or the absence of negative charge at the centre or surface (as in Ga$_{18}$Al$_2$$^+$). Moreover, for Ga$_{13}$Al$_7$$^+$, Ga$_{12}$Al$_8$$^+$ and GaAl$_{19}$$^+$, along with the monometallic Ga\textsubscript{20}\textsuperscript{+} and Al\textsubscript{20}\textsuperscript{+} clusters, there is no negatively charged surface atom. Strong charge segregation between the internal and surface sites plays an important role in the greater-than-bulk melting behaviour as also reflected by the diffusion coefficients (Fig.~\ref{DC}) of the representative clusters\cite{selfAl}.

The average coordination number, diffusion coefficient and atoms-in-molecules analysis bring out the differences between the internal and surface sites in  these clusters. The internal atoms being confined in an electrostatic cage, breaking of which leads to the solid-liquid-like phase transition in Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} clusters, is a physical picture which can help explain the \textit{greater-than-bulk melting character} (GB) of this system. Greater-than-bulk melting behaviour, observed in gallium\cite{jarrold_GaPRL} and tin\cite{jarrold_tin} clusters, is an exception to the melting point depression with size as predicted by Pawlow\cite{pawlow}. Models typically applied to understand the size dependence of the phase transition in clusters\cite{pd4,bulk2} have expressed the cluster melting temperature as a function of the bulk melting temperature with a parameter catering for the size dependence component (where the nanoparticle is generally assumed spherical). Although this may be a reasonable approximation for cluster sizes having hundreds of atoms, a plethora of research currently addresses the different spatial geometries assumed by the putative global minimum structures of nanoparticles having fewer than tens of atoms\cite{baletto,nanoalloys}.

How different is a gallium-aluminium nanoalloy cluster from the corresponding bulk alloy material? Taking into account the GB character, energy of mixing and the associated intrinsic elemental character (to be common in bulk and cluster), we have attempted to provide a simplistic view of the Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} cluster system. Our contention is that a cluster can be viewed as a piece of the bulk matter with additional properties specific to a particular cluster size, as expressed in Eq.~\ref{model} for our specific case. Our intention is two-fold: firstly, to find a way to `quantify' the inherent and size dependent GB character among Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} clusters and, secondly to compare the obtained melting temperature from Eq.~\ref{model} with those obtained from our DFT calculations to gauge the applicability of this picture.
\begin{multline}
T_{m} (Ga_{(20-x)}Al_{x}^{+}) = T_{bulk} (Ga:Al :: (20-x):x) \\
	+ \nu_{GB} + \nu_{exc}
\label{model}
\end{multline}
Here T\textsubscript{m} and T\textsubscript{bulk} are the cluster and bulk alloy melting temperatures for similar composition and $\nu_{GB}$, $\nu_{exc}$ are the functions representing the contributions of the greater-than-bulk melting character and the energy of mixing respectively.

To `quantify' the GB character, we revert back to the picture of the internal atoms which are confined in an electrostatic cage by the surface atoms in Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} clusters, disruption of which is required for melting. We view this difference in the environments of the internal and surface atoms as an `energy barrier' which exists between the internal and surface sites. With increasing temperature, the internal and surface atoms have enough energy to cross this existing `energy barrier' and thus either replace each other or independently become a surface or internal atom which subsequently leads to a change in their respective mobilities in their new sites below the melting temperature. This change in the cluster either due to a change in the number of internal atoms or the type of internal atom (considering swapping of atoms due to parallel tempering or an exchange of positions between the internal and surface atoms) is, from here onwards, termed as \textit{`Change-Swap (CS)'}. Characterising the \textit{liquid-like} state as one where all the atoms have an equal likelihood of occupying an internal or surface site, we have attempted to understand the strength of the `energy barrier' among the five representative structures in Ga$_{(20-x)}$Al$_{x}$$^+$ series through an \textit{Arrhenius-like} equation, Eq.~\ref{Arrh}, which is also used to describe diffusion.
\begin{equation}
ln~k_{CS} = ln~A  - {E_{barrier}}\cdot(\frac{1}{T})
\label{Arrh}
\end{equation}
Here, $k_{CS}$ is the rate constant in ns$^{-1}$, A is the pre-exponential factor, T is the temperature in Kelvin and $E_{barrier}$ characterizes the energy barrier between the internal and surface sites. The ratio of total number of times a CS occurs to the total MD trajectory length would give the rate of exchange ($k_{CS}$) at each temperature. This allows us a way of using $E_{barrier}$ as a quantifiable `measure' of the strength between the core (internal atoms) and surface atoms i.e. an intrinsic, cluster-dependent and intensive quantity which could be correlated with the \textit{greater-than-bulk melting} character ($\nu_{GB}$).

Shown in the inset of Fig.~\ref{Arrhenius}  are the data points and the corresponding linear least squares fit based on the \textit{`persistent internal} atom criterion \textit{(a)'}. We observe stronger fluctuations in the natural logarithm of the CS rate below the melting temperature and thus decided to perform the least squares fit to data points above the melting temperature. The obtained $E_{barrier}$ values from the fit has been tabulated in Table~\ref{ebarrier_table}. Although we do observe a clear increase in the energy barrier with increasing Al atoms in the Ga$_{(20-x)}$Al$_{x}$$^+$ cluster series, we found the \textit{`persistent internal'} atom criterion \textit{(a)} quite loose for the temperatures below the melting temperature for tagging an atom to be \textit{internal}. The high mobility of the surface atoms led to frequent expansion and shrinkage of the cluster volume as observed in the MD. Thus, although when observed over a time range as in criterion (b), the \textit{`persistent internal'} atom does extremely well to tag a particular atom as internal, it needs further refining when monitoring changes at every time step. Furthermore, from MD observations we found two ways in which the internal and surface atoms and sites were exchanged: (i) stage-wise where a surface atom became internal in subsequent MD steps, and (ii) due to parallel tempering. With increasing temperatures, we also observed changes in the number of internal and surface atoms reflecting presence of isomeric structures near the melting temperatures. We detail our observations from the MD movies in section 3 (Supplementary Information).

\begin{figure}[t!]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true,width=\columnwidth]{percentCS_new.eps}
\caption{Rate of change-swap (CS) between the internal and external atoms in the representative Ga$_{(20-x)}$Al$_{x}$$^+$ clusters. The temperatures at which the rate of CS was calculated is written above the bars.}
\label{percent}
\end{figure}

 \begin{figure}[t!]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true,width=\columnwidth]{Arr_old_new.eps}
\caption{Arrhenius plot showing the dependence of natural logarithm of the rate of CS between the internal and surface sites to the inverse of temperature. The dashed lines are the least-square straight line fits to the data points obtained from the convex hull method. The inset shows the corresponding data points obtained from the \textit{persistent internal} atom criterion (\textit{a}). The line fit has been done only for temperatures above the melting point for each cluster.}
\label{Arrhenius}
\end{figure}

To counter the problem of accurately tagging a particular atom as \textit{internal} at each MD step, we employed the convex hull technique\cite{convexhull} which for a finite set of points (in this case 20) is the union of all convex combinations of them. For each configuration of 20 points, we perform the convex hull in both two and three dimensions. In three dimensions, we disregard the atoms which form the vertices of the hull. In the two dimensions, we calculate the convex hull for the top view, front view and side view of the cluster. A cartesian coordinate (atomic site) is considered \textit{internal} if it is a non-hull vertex in all the three respective two dimensional convex hulls along with being a non-hull vertex in the corresponding three dimensional convex hull also satisfying the criterion \textit{(a)} of the \textit{`persistent internal'} atom.

\begin{table}[b]
\centering
\caption{Comparison of the $E_{barrier}$ values obtained using the two methods described above.}
\begin{tabular}{c c c}
\hline
\hline
 & \textit{`Persistent internal'} & Convex hull\\
 & atom criterion \textit{(a)} & method\\
 \hline
Ga$_{20}^{+}$ & 729.5 & 2165.6\\
Ga\textsubscript{19}Al\textsuperscript{+} & 1306.5 & 3301.4\\
Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} & 1433.9 & 3767.3 \\
Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+} & 2570.2 & 3921.3 \\
Al\textsubscript{20}\textsuperscript{+} & 2889.5 & 3982.3 \\
\hline
\end{tabular}
\label{ebarrier_table}
\end{table}

Fig~\ref{percent} shows the rate of CS for the representative clusters during the microcanonical simulations, at average  temperatures below the melting temperature, above the melting temperature and at the highest energy simulated in which case all clusters are fully \textit{liquid-like}. We have ignored those CS brought about by parallel tempering where there is a change only in the number of internal sites (isomeric) as opposed to the atom occupying the internal site as well (homotopic). In all cases, we see an increase in the rate of CS with temperature. However, we also observe that below the melting temperature the rate of CS is dependent on the amount of mixing among representative clusters.

\begin{figure}[t]
\centering
\includegraphics[trim = 0cm 0cm 0cm 0cm,clip=true,width=\columnwidth]{model_shaded_final.eps}
\caption{Comparison of the DFT calculated cluster melting temperature (red) of the five representative compositions of Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} cluster system to that obtained considering the picture described in Eq.~\ref{model}.}
\label{model_pic}
\end{figure}

Shown in Fig.~\ref{Arrhenius} is the corresponding natural logarithm of the rate of CS calculated at average temperatures for different microcanonical trajectories. The temperatures for which CS was less than 10 discrete instances during the MD trajectory, or the contribution of PT to CS was more than 15\% have been discarded, leaving a minimum of eight data points. Shown as dashed lines are the corresponding linear least squares line fit to the values. Comparing to the inset of Fig.~\ref{Arrhenius}, we observe that the spread in data at temperatures below the melting temperature has been significantly reduced, reflecting the importance of added screening to gauge a CS situation. The slopes of the line-fit, i.e. $E_{barrier}$ for the different clusters, have been tabulated in Table~\ref{ebarrier_table}. We find that with increasing Al content in the cluster, the energy barrier for a CS situation increases. It must however be noted that the actual magnitude of $E_{barrier}$ depends not only on the number of data points and thus the fitting itself but also the method used to calculate the rate of CS. From Table~\ref{ebarrier_table}, correlating with the $\Delta T_m$ values tabulated in Table~\ref{melttemp}, we observe that there is an inverse relationship between the relative temperature difference between the cluster and the corresponding bulk Ga-Al alloy and the greater-than-bulk melting character (GB).

Expressing $\nu_{GB} = \alpha f(E_{barrier})$, we first perform a linear least squares fit to the $E_{barrier}$ values obtained using the convex hull method for the pure phases, and follow by optimising $\alpha$. Represented as green triangles we show in Fig.~\ref{model_pic} the obtained melting temperatures of the five representative clusters when GB character has been added to the bulk melting temperatures. Furthermore, we express $\nu_{exc} = \beta E_{exc}$ and thereby correct the melting temperatures of the mixed phases which are now within 2\% error from the DFT calculated (red circles) melting temperatures, shown as blue triangles in Fig.~\ref{model_pic}.

\section{Conclusion}
First principles calculations predict greater-than-bulk melting behaviour for the mixed gallium-aluminium bimetallic clusters: Ga\textsubscript{11}Al\textsubscript{9}\textsuperscript{+} and Ga\textsubscript{3}Al\textsubscript{17}\textsuperscript{+}. This behaviour has already been observed experimentally for Ga\textsubscript{20}\textsuperscript{+} \& Ga\textsubscript{19}Al\textsuperscript{+} and predicted for Al\textsubscript{20}\textsuperscript{+}. Moreover, the melting temperature of the Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} nanoalloys increases with increasing Al content. The differences between the environments of internal and surface sites of the mixed clusters has been convincingly demonstrated, a feature which seems common to the Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} cluster series. An Arrhenius-like analysis describes this difference as an energy barrier which gives a way to quantify the greater-than-bulk melting character of these nanoalloys. Furthermore, we propose a picture where the  Ga\textsubscript{(20-x)}Al\textsubscript{x}\textsuperscript{+} clusters are viewed as components of the corresponding bulk alloy phase with a systematic increase in the melting temperature which can be ascribed to this finite size specific energy barrier.

\section{Acknowledgement}
The support of Royal Society of New Zealand (RSNZ) through the Marsden Fund (contract no. IRL0801) and New Zealand e-Science Infrastructure (NeSI) for computational resources is gratefully acknowledged. We would also like to thank Krista G. Steenbergen for useful discussions.

redpajama_set_name: RedPajamaArXiv


text:
Medicines breakthrough: Pharma payments to doctors disclosed
1 September 2016 — Media release
The identification of thousands of doctors receiving payments from pharmaceutical companies is a landmark advance towards transparency in health care, the Consumers Health Forum says.
"The voluntary disclosure of the names of doctors and others who have received significant payments for talking about pharmaceuticals opens up these once-hidden transactions to public scrutiny and that is an important development for health consumers" the CEO of the Consumers Health Forum, Leanne Wells, said.
"While there was resistance in some quarters of the medical profession to the move to individual disclosure, we congratulate the many doctors who have voluntarily declared the payments.
"This is a further vital step in the lifting of the shroud which often obscures the inner workings and payments of the health system.
"It is very much in the consumer's interests that payments from drug companies and any other firms to health practitioners are on the public record.
"Evidence-based medicine is a central feature of our health care. It makes sense that any payments concerning education and promotion about drugs are out in the open because we don't want consumers to be prescribed medicines on grounds other than what is in the best interests of their health.
"This opening up is the result of gradual moves by the ACCC and the industry body, Medicines Australia, to progressively strengthen its code of conduct to meet stronger standards of transparency.
"This will take a further step forward when the disclosure of payments will become mandatory for the next report.
"There remains however a significant area where perks to doctors remain undisclosed. Doctors can still receive meals valued at up to $120 paid for by drug companies without disclosure.
"That leaves considerable scope for benefits to doctors by pharmaceutical reps making their routine visits to practices.
"While many doctors have argued they are not swayed by drug company perks, research shows otherwise.
"A new study published in the Journal of the American Medical Association for instance found that doctors who receive a single inexpensive meal from a drug company tend to prescribe a lot more of that company's products.
"The Consumers Health Forum believes it would be in the interests of healthy medicines policy for annual limits to be placed on the value of meals for doctors," Ms Wells said.
For links to each of the pharmaceutical companies pages that discloses their payments to healthcare professionals, see this page on the Medicines Australia website.
https://medicinesaustralia.com.au/code-of-conduct/education-events-reports/payments-to-healthcare-professionals/member-company-reports/
20160901_medicines_breakthrough_doctors_disclose_drug_company_payments.pdf (131.63 KB)

redpajama_set_name: RedPajamaCommonCrawl


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3) Describe problem: I am using the script in several places in a table but the problem I am having is when I have a link near the right end of the table cell the hint displays partway the rest is lost off the cell/table/page. Is there a way to change the script to tell it to diaplay left or right of the anchor.
The script should reposition itself horizontally if too close to the window's right edge. Please post a link to the page on your site that contains the problematic script so we can check it out.


I've never read Fahrenheit 451.
But when I saw the 5-disc audiobook, narrated by the lovely and talented Scott Brick, I picked it up.
This story's famous premise takes place in a not-too-distant future in which firemen are in charge of starting fires to destroy books, rather than putting fires out. Guy Montag, a fireman, slowly becomes disillusioned with his job and his happiness when he meets Clarisse, a neighbor girl who seems to think beyond the parameters they all live by.
This still stands as a classic in literature, and is, ironically, often found on banned book lists.
I'm glad I read this!


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2016/01/01 Time: 02:16:00 Date: 2016/01/01 Time: 02:20:00 Date: 2016/01/01 Time: 02:24:00 Date: 2016/01/01 Time: 02:28:00 Date: 2016/01/01 Time: 02:32:00 Date: 2016/01/01 Time: 02:36:00 Date: 2016/01/01 Time: 02:40:00 Date: 2016/01/01 Time: 02:44:00 Date: 2016/01/01 Time: 02:48:00 Date: 2016/01/01 Time: 02:52:00 Date: 2016/01/01 Time: 02:56:00 Date: 2016/01/01 Time: 03:00:00 Date: 2016/01/01 Time: 03:04:00 Date: 2016/01/01 Time: 03:08:00 Date: 2016/01/01 Time: 03:12:00 Date: 2016/01/01 Time: 03:16:00 Date: 2016/01/01 Time: 03:20:00 Date: 2016/01/01 Time: 03:24:00 Date: 2016/01/01 Time: 03:28:00 Date: 2016/01/01 Time: 03:32:00 Date: 2016/01/01 Time: 03:36:00 Date: 2016/01/01 Time: 03:40:00 Date: 2016/01/01 Time: 03:44:00 Date: 2016/01/01 Time: 03:48:00 Date: 2016/01/01 Time: 03:52:00 Date: 2016/01/01 Time: 03:56:00 Date: 2016/01/01 Time: 04:00:00 Date: 2016/01/01 Time: 04:04:00 Date: 2016/01/01 Time: 04:08:00 Date: 2016/01/01 Time: 04:12:00 Date: 2016/01/01 Time: 04:16:00 Date: 2016/01/01 Time: 04:20:00 Date: 2016/01/01 Time: 04:24:00 Date: 2016/01/01 Time: 04:28:00 Date: 2016/01/01 Time: 04:32:00 Date: 2016/01/01 Time: 04:36:00 Date: 2016/01/01 Time: 04:40:00 Date: 2016/01/01 Time: 04:44:00 Date: 2016/01/01 Time: 04:48:00 Date: 2016/01/01 Time: 04:52:00 Date: 2016/01/01 Time: 04:56:00 Date: 2016/01/01 Time: 05:00:00 Date: 2016/01/01 Time: 05:04:00 Date: 2016/01/01 Time: 05:08:00 Date: 2016/01/01 Time: 05:12:00 Date: 2016/01/01 Time: 05:16:00 Date: 2016/01/01 Time: 05:20:00 Date: 2016/01/01 Time: 05:24:00 Date: 2016/01/01 Time: 05:28:00 Date: 2016/01/01 Time: 05:32:00 Date: 2016/01/01 Time: 05:36:00 Date: 2016/01/01 Time: 05:40:00 Date: 2016/01/01 Time: 05:44:00 Date: 2016/01/01 Time: 05:48:00 Date: 2016/01/01 Time: 05:52:00 Date: 2016/01/01 Time: 05:56:00 Date: 2016/01/01 Time: 06:00:00
End Time: Date: 2015/12/31 Time: 18:00:00 Date: 2015/12/31 Time: 18:04:00 Date: 2015/12/31 Time: 18:08:00 Date: 2015/12/31 Time: 18:12:00 Date: 2015/12/31 Time: 18:16:00 Date: 2015/12/31 Time: 18:20:00 Date: 2015/12/31 Time: 18:24:00 Date: 2015/12/31 Time: 18:28:00 Date: 2015/12/31 Time: 18:32:00 Date: 2015/12/31 Time: 18:36:00 Date: 2015/12/31 Time: 18:40:00 Date: 2015/12/31 Time: 18:44:00 Date: 2015/12/31 Time: 18:48:00 Date: 2015/12/31 Time: 18:52:00 Date: 2015/12/31 Time: 18:56:00 Date: 2015/12/31 Time: 19:00:00 Date: 2015/12/31 Time: 19:04:00 Date: 2015/12/31 Time: 19:08:00 Date: 2015/12/31 Time: 19:12:00 Date: 2015/12/31 Time: 19:16:00 Date: 2015/12/31 Time: 19:20:00 Date: 2015/12/31 Time: 19:24:00 Date: 2015/12/31 Time: 19:28:00 Date: 2015/12/31 Time: 19:32:00 Date: 2015/12/31 Time: 19:36:00 Date: 2015/12/31 Time: 19:40:00 Date: 2015/12/31 Time: 19:44:00 Date: 2015/12/31 Time: 19:48:00 Date: 2015/12/31 Time: 19:52:00 Date: 2015/12/31 Time: 19:56:00 Date: 2015/12/31 Time: 20:00:00 Date: 2015/12/31 Time: 20:04:00 Date: 2015/12/31 Time: 20:08:00 Date: 2015/12/31 Time: 20:12:00 Date: 2015/12/31 Time: 20:16:00 Date: 2015/12/31 Time: 20:20:00 Date: 2015/12/31 Time: 20:24:00 Date: 2015/12/31 Time: 20:28:00 Date: 2015/12/31 Time: 20:32:00 Date: 2015/12/31 Time: 20:36:00 Date: 2015/12/31 Time: 20:40:00 Date: 2015/12/31 Time: 20:44:00 Date: 2015/12/31 Time: 20:48:00 Date: 2015/12/31 Time: 20:52:00 Date: 2015/12/31 Time: 20:56:00 Date: 2015/12/31 Time: 21:00:00 Date: 2015/12/31 Time: 21:04:00 Date: 2015/12/31 Time: 21:08:00 Date: 2015/12/31 Time: 21:12:00 Date: 2015/12/31 Time: 21:16:00 Date: 2015/12/31 Time: 21:20:00 Date: 2015/12/31 Time: 21:24:00 Date: 2015/12/31 Time: 21:28:00 Date: 2015/12/31 Time: 21:32:00 Date: 2015/12/31 Time: 21:36:00 Date: 2015/12/31 Time: 21:40:00 Date: 2015/12/31 Time: 21:44:00 Date: 2015/12/31 Time: 21:48:00 Date: 2015/12/31 Time: 21:52:00 Date: 2015/12/31 Time: 21:56:00 Date: 2015/12/31 Time: 22:00:00 Date: 2015/12/31 Time: 22:04:00 Date: 2015/12/31 Time: 22:08:00 Date: 2015/12/31 Time: 22:12:00 Date: 2015/12/31 Time: 22:16:00 Date: 2015/12/31 Time: 22:20:00 Date: 2015/12/31 Time: 22:24:00 Date: 2015/12/31 Time: 22:28:00 Date: 2015/12/31 Time: 22:32:00 Date: 2015/12/31 Time: 22:36:00 Date: 2015/12/31 Time: 22:40:00 Date: 2015/12/31 Time: 22:44:00 Date: 2015/12/31 Time: 22:48:00 Date: 2015/12/31 Time: 22:52:00 Date: 2015/12/31 Time: 22:56:00 Date: 2015/12/31 Time: 23:00:00 Date: 2015/12/31 Time: 23:04:00 Date: 2015/12/31 Time: 23:08:00 Date: 2015/12/31 Time: 23:12:00 Date: 2015/12/31 Time: 23:16:00 Date: 2015/12/31 Time: 23:20:00 Date: 2015/12/31 Time: 23:24:00 Date: 2015/12/31 Time: 23:28:00 Date: 2015/12/31 Time: 23:32:00 Date: 2015/12/31 Time: 23:36:00 Date: 2015/12/31 Time: 23:40:00 Date: 2015/12/31 Time: 23:44:00 Date: 2015/12/31 Time: 23:48:00 Date: 2015/12/31 Time: 23:52:00 Date: 2015/12/31 Time: 23:56:00 Date: 2016/01/01 Time: 00:00:00 Date: 2016/01/01 Time: 00:04:00 Date: 2016/01/01 Time: 00:08:00 Date: 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2016/01/01 Time: 02:16:00 Date: 2016/01/01 Time: 02:20:00 Date: 2016/01/01 Time: 02:24:00 Date: 2016/01/01 Time: 02:28:00 Date: 2016/01/01 Time: 02:32:00 Date: 2016/01/01 Time: 02:36:00 Date: 2016/01/01 Time: 02:40:00 Date: 2016/01/01 Time: 02:44:00 Date: 2016/01/01 Time: 02:48:00 Date: 2016/01/01 Time: 02:52:00 Date: 2016/01/01 Time: 02:56:00 Date: 2016/01/01 Time: 03:00:00 Date: 2016/01/01 Time: 03:04:00 Date: 2016/01/01 Time: 03:08:00 Date: 2016/01/01 Time: 03:12:00 Date: 2016/01/01 Time: 03:16:00 Date: 2016/01/01 Time: 03:20:00 Date: 2016/01/01 Time: 03:24:00 Date: 2016/01/01 Time: 03:28:00 Date: 2016/01/01 Time: 03:32:00 Date: 2016/01/01 Time: 03:36:00 Date: 2016/01/01 Time: 03:40:00 Date: 2016/01/01 Time: 03:44:00 Date: 2016/01/01 Time: 03:48:00 Date: 2016/01/01 Time: 03:52:00 Date: 2016/01/01 Time: 03:56:00 Date: 2016/01/01 Time: 04:00:00 Date: 2016/01/01 Time: 04:04:00 Date: 2016/01/01 Time: 04:08:00 Date: 2016/01/01 Time: 04:12:00 Date: 2016/01/01 Time: 04:16:00 Date: 2016/01/01 Time: 04:20:00 Date: 2016/01/01 Time: 04:24:00 Date: 2016/01/01 Time: 04:28:00 Date: 2016/01/01 Time: 04:32:00 Date: 2016/01/01 Time: 04:36:00 Date: 2016/01/01 Time: 04:40:00 Date: 2016/01/01 Time: 04:44:00 Date: 2016/01/01 Time: 04:48:00 Date: 2016/01/01 Time: 04:52:00 Date: 2016/01/01 Time: 04:56:00 Date: 2016/01/01 Time: 05:00:00 Date: 2016/01/01 Time: 05:04:00 Date: 2016/01/01 Time: 05:08:00 Date: 2016/01/01 Time: 05:12:00 Date: 2016/01/01 Time: 05:16:00 Date: 2016/01/01 Time: 05:20:00 Date: 2016/01/01 Time: 05:24:00 Date: 2016/01/01 Time: 05:28:00 Date: 2016/01/01 Time: 05:32:00 Date: 2016/01/01 Time: 05:36:00 Date: 2016/01/01 Time: 05:40:00 Date: 2016/01/01 Time: 05:44:00 Date: 2016/01/01 Time: 05:48:00 Date: 2016/01/01 Time: 05:52:00 Date: 2016/01/01 Time: 05:56:00 Date: 2016/01/01 Time: 06:00:00
Stride (skip time steps): 0 1 2 3 4
Email address for notification (replace the example email address with yours):
Note: The movie will be requested but NOT be shown in this interface. You will get an email with a download URL when the request has been completed (this will take at least a few minutes).
Only one request can be pending at a time for each client IP or email address. Movies and Images remains on the ftp server for a week and need to be downloaded within that time.
Choose Plot Mode:
Surface Plot (2D) Line (1D) Contour (2D) Vector (2D) ColorContour (2D) Color+Vector Contour+Vector Color+Contour Color+Vector+Contour Color+Vector+Flowlines 3D Flowlines ColorContour on Sphere ColorContour+Vector on Sphere
Plot Options:
Exclude region around the Earth up to RE (this radius value is also used by the Color Contour on Sphere plot)
Image magnification 0.75 1 1.25 1.5 2
(all images; use >=1.25 for 3D Flowlines)
Line thickness 1 2 3 4 (flow lines, arrows)
Character thickness 1 2 3 (all annotations)
Allow variable plot image size
(all 2D plots: aspect ratio dx/dy between 0.3 and 4)
Show simulation grid (disabled with 3D-Surface)
Show boundary of closed field lines (magnetopause on dayside) Positions in 2D cuts passing within 12 RE of Earth will be listed at the bottom.
Tolerance (between 0.01 and 1 RE):
Maximum Azimuth from Sun direction (≥q;0.25 degrees, ≤q;180 degrees):
Angular Resolution (≥q;0.25 degrees, ≤q; Maximum Azimuth):
Show magnetic topology (use with "ColorContour", "Color+Vector" plot modes:
Add color coding by magnetic connectivity: red: closed, blue, open, yellow: connected to north, green: connected to south)
Display Contour data with topology plot
Elements in base grid from which field lines emanate:
Base grid size
Horizontal N1: (between 5 and 11):
Vertical N2: (between 5 and 11):
Refine base grid by 2Adaptation, computation time for this will scale accordingly:
Adaptation: (between 2 and 6):
Render grid cell vertices (to see positions used). Do not use with adapt ≥ 4, since PostScript (EPS) images can become very large.
Interpolate data onto equidistant grid (available with 3D-Surface and Vector; recommended for plots with Vector)
New: Add satellite position to plot:
Cluster-1 (FM5/Rumba) Cluster-2 (FM6/Salsa) Cluster-3 (FM7/Samba)
Cluster-4 (FM8/Tango) Geotail GOES-11
GOES-12 GOES-13 GOES-14
GOES-15 GOES-8 LRO
MMS 1 MMS 2 MMS 3
MMS 4 Moon RBSP-A
RBSP-B SDO THEMIS-A (P5)
THEMIS-B (P1) THEMIS-C (P2) THEMIS-D (P3)
THEMIS-E (P4) Twins1 Twins2
XMM-Newton
Note: Satellite positions are projected onto the selected cut plane if within the selected plot area.
Satellite positions may be far away from the selected cut plane.
The two Artemis satellites (P1,P2) are listed under the original Themis mission name.
Choose quantity to be displayed (some Plot Modes require up to three choices):
Q 1: B_x B_y B_z V_x V_y V_z N P Eta B1_x B1_y B1_z J_x J_y J_z B beta V J B1 BA theta_stretch B_r B_t B_p V_r V_t V_p J_r J_t J_p gradN_x gradN_y gradN_z gradN E_x E_y E_z E T S P_ram V_A M_A J_par_x J_par_y J_par_z J_par JxB_x JxB_y JxB_z JxB ExB_x ExB_y ExB_z ExB div.ExB E.J etaJ_x etaJ_y etaJ_z etaJ etaJ2 omega_pi omega_pe NV_x NV_y NV_z NV div.NV div.V div.B div.B1 gradP_x gradP_y gradP_z gradP gradT_x gradT_y gradT_z gradT gradBeta_x gradBeta_y gradBeta_z gradBeta omega_x omega_y omega_z omega curlJ_x curlJ_y curlJ_z curlJ omega.B V.J custom
(select 'custom' above): C1=M_A/(sqrt(sqrt(1+beta)+1)) ; [] C2=sqrt(T/11604.)/N ; [sqrt(eV)cm^3] C3=ExB/(1e-9*B*B) ; [km/s] Q 2: B_x B_y B_z V_x V_y V_z N P Eta B1_x B1_y B1_z J_x J_y J_z B beta V J B1 BA theta_stretch B_r B_t B_p V_r V_t V_p J_r J_t J_p gradN_x gradN_y gradN_z gradN E_x E_y E_z E T S P_ram V_A M_A J_par_x J_par_y J_par_z J_par JxB_x JxB_y JxB_z JxB ExB_x ExB_y ExB_z ExB div.ExB E.J etaJ_x etaJ_y etaJ_z etaJ etaJ2 omega_pi omega_pe NV_x NV_y NV_z NV div.NV div.V div.B div.B1 gradP_x gradP_y gradP_z gradP gradT_x gradT_y gradT_z gradT gradBeta_x gradBeta_y gradBeta_z gradBeta omega_x omega_y omega_z omega curlJ_x curlJ_y curlJ_z curlJ omega.B V.J custom
(select 'custom' above): C1=M_A/(sqrt(sqrt(1+beta)+1)) ; [] C2=sqrt(T/11604.)/N ; [sqrt(eV)cm^3] C3=ExB/(1e-9*B*B) ; [km/s]
Want to see more custom variables?
Email the formula that you would like to see and that uses existing quantities to Lutz and it will be tested and added.
Plot Options for selected Plot Modes:
3D-Surface, 3D-Flowlines, Color Contour on Sphere:
View angles:
AX [-90..90]: (viewer's elevation angle)
AZ [-180 ... 180]: (viewer's azimuth angle; 0: along negative Y)
Color Contour, (Vertical) Line:
Color table: B-W LINEAR BLUE/WHITE GRN-RED-BLU-WHT RED TEMPERATURE BLUE/GREEN/RED/YELLOW STD GAMMA-II PRISM RED-PURPLE GREEN/WHITE LINEAR GRN/WHT EXPONENTIAL GREEN-PINK BLUE-RED 16 LEVEL RAINBOW STEPS STERN SPECIAL Haze Blue - Pastel - Red Pastels Hue Sat Lightness 1 Hue Sat Lightness 2 Hue Sat Value 1 Hue Sat Value 2 Purple-Red + Stripes Beach Mac Style Eos A Eos B Hardcandy Nature Ocean Peppermint Plasma Blue-Red Rainbow Blue Waves Volcano Waves Rainbow18 Rainbow + white Rainbow + black gsfc2-95 B-W LINEAR+colors blue-white-red
Reverse Colortable
Number of levels: 16 32 64 128 256
Lock color range:
Min.: Max.:
Log scale (use all data>0 in non-negative fields)
Contour:
show values with contour levels
16 32 64 128 256 Number of Levels
Lock range:
Vector:
length of arrows: 0.3 1.0 3.0 10
Normalize arrow length
Unit arrow length at:
Log scale (scale arrows logarithmically)
3D-Flowlines:
flowline start positions
Choose Flowline Setup Mode: only user-defined start points predefined in 3D (V,B,other) random in 3D - uniform random in 3D - concentrated in center of box predefined in cut plane uniform random in cut plane random in cut plane - concentrated in center
user-defined flowline start positions:
Choose Plot Area:
All Plot Modes except Line Plot and Vertical Plot: Select lower left corner of plot area on the left, and the upper right corner on the right.
Line Plot: Select start point of line on the left, the end point on the right.
Vertical Plot: Select X and Y position on the left. Choose Cut Plane:
X1 X2 Range: -350.01 ... 33.01 RE X=constant
Y1 Y2 Range: -48.01 ... 48.01 RE Y=constant
Z1 Z2 Range: -48.01 ... 48.01 RE Z=constant
New: Oblique cut plane
Render Oblique Cut Plane (2D Plot Modes)
Coordinate system: SM GSM GSE
Normal Vector (N): X: Y: Z:
Distance from Origin along Normal (DO): RE
Normal vectors for axis-parallel cut slices aligned with coordinate axes: X=const: [1,0,0]; Y=const: [0,-1,0]; Z=const: [0,0,1]
ξ-direction is along (Z-axis x N) or if N∥(Z-axis) along (Y-axis x N)
Local Time: (Local time applies for ξ>0, plane through origin, ζ axis along Z axis of selected coordinate system)
Plot area: Horizontal: ξ1: ξ2:
Vertical: ζ1: ζ2:
Update Plot will update (generate) the plot with the chosen time and plot parameters above.
List Data (check to get any of the following outputs which apply to movie requests as well):
What: Plot variables from above
Include all primary model output parameters (Warning: text files may become large).
You have to select vector magnitudes (e.g., "B","V","J") explicitly for plotting to get them:
computed scalars such as
derived vectors (e.g, "JxB"): select one component or its magnitude to get all components
Include parameters from this list in addition to those selected for the plot: (copy names from Q1 list above and separate them with commas).
Where: At positions specified: enter positions in X, Y, Z, (within the allowed range) as comma-separated lists.
Use combination of positions in a 3D grid.
X positions:
Y positions:
Z positions:
List Data From Plot:
2D plots (Contour, Vector, ...):
equidistant 61x61-element grid in cut plane (Interpolate data onto equidistant grid selected)
max. 44000 grid positions (Interpolate data onto equidistant grid unchecked)
LinePlot: data along line plotted,
Text output: start and end points of flow lines with topology and exit status of line segment tracings,
Tar archive: model output data along flowlines with user-defined start points.


As early as in the third quarter of 201, the niche sports brand Ashton Martin launches its latest model, the DBS Superleggera. The new creation of the brand will be added to the group of the fastest sports cars with a classic powertrain. What's worth knowing today? This new, great car has a V12 engine with a capacity of 5.2 litres.
This, of course, translates into the speed, the heart of every sports car. The powerful engine develops its maximum power at 6500 rpm and has a torque of 900 Nm. The DBS Superlegger accelerates to 100 km/h in an incredible 3.4 seconds. The time to change speed from 80 km/h to 160 km/h is also stunning - it's only 4.2 seconds. The manufacturer claims that this is the best performance in this class of cars (which also includes the Ferrari 812 Superfast and the Chevrolet Corvette ZR1). Also noteworthy is the careful alignment of the sounds of the exhaust system with the flaps. The rear-wheel drive is provided by an eight-speed automatic, and the car also features a torque vectoring differential that effectively reduces slippage.
What is characteristic of a good sports car is suspension. On the Aston Martin, the DBS Superleggera is made of forged aluminium with adaptive shock absorbers. It also allows you to choose between three driving and customisation modes - GT, Sport and Sport Plus. The car does not have too big a sash, but the body at maximum speed (340 km/h) generates as much as 180 kg of pressure. It is also equipped with a double diffuser. What else to know about DBS Superlegger? It is 5 mm smaller than the DB11, with Pirelli 265/35 R21 tyres at the front and 305/30 R21 at the rear, with a carbon-ceramic brake disc diameter of 410 and 350 mm and a coupé weighing just 1690 kg.
The airflow solutions used in this model also deserve attention. Aston Martin is clearly focused on the flow underneath the car, while at the same time reducing the resistance in the upper part of the car. Thanks to the large air outlets behind the front wheels, Aston has avoided the shockwave effect, which often occurs at high speeds.
The development of the DBS Superlegger was accompanied by the intention of designing a sports car that will introduce beginners to the world of fast driving, but it is also impossible to be bored by the more familiar. Although it sounds like a compromise, in this case it did not hurt - the car works very well.
The interior of the new model resembles the well-known DB11, but some important details have changed here. First of all, the manufacturer relies on luxurious materials to distinguish his car from similar proposals of competing brands. The DBS Superleggera is not only to serve as an adrenaline-producing car, but also as an extremely comfortable and exclusive one. Attentive observers will certainly not escape the effect of cooperation with Mercedes in the form of a multimedia system interface.
How much does it cost a new miracle in the sports motoring market? In Germany, a price of EUR 274 995 was set for it.


Hyundai has tinkered with the names of its mid-size and full-size SUVs for the 2019 model year. The redesigned two-row 2019 Santa Fe reviewed here replaces the Santa Fe Sport in Hyundai's lineup, and the three-row Santa Fe has been dubbed Santa Fe XL for 2019 but is a carryover model with few changes. The Santa Fe XL isn't long for this world, though; it's slated to be replaced by the three-row Hyundai Palisade, which will arrive next summer as a 2020 model.
The 2019 Santa Fe's profile looks more upright than the outgoing Santa Fe Sport's, with a windshield that's not as raked. It looks more like an SUV now, and one big practical advantage of the design is good visibility: Thin front roof pillars and side mirrors mounted on the front doors (rather than the base of those pillars) help give the Santa Fe great forward views. Hyundai also flattened out the SUV's beltline, increasing visibility for rear passengers and providing better over-shoulder views for the driver.
The Santa Fe's front end is, without question, the most polarizing aspect of the design. Like Hyundai's subcompact Kona SUV and upcoming three-row Palisade, the Santa Fe has slim LED daytime running lights that sit below the front edges of the hood and flank a gaping grille (the headlights sit below the DRLs). It's not a new design tactic — the pre-2019 Jeep Cherokee had something similar — but it's an approach that's gaining steam; the upcoming 2019 Blazer also uses it.
The Santa Fe is composed and comfortable in the city and on rural two-lane highways, but it's flustered by more challenging, twisty roads. Some drivetrain-tuning choices also hurt the driving experience.
The standard 2.4-liter four-cylinder engine makes adequate power, but full-throttle acceleration is modest. The engine works with an eight-speed automatic transmission that kicks down quickly but isn't always willing to select as low a gear as is needed.
Gas-pedal response is gradual in the Comfort drive mode, but you get used to it after a while. The Sport mode, however, isn't great in everyday driving; it makes the gas pedal extremely sensitive, to the point that it's hard to accelerate smoothly or hold a steady speed.
The Santa Fe's suspension is comfort-oriented without feeling floaty, which seems like the right approach for this class.
The optional turbo 2.0-liter four-cylinder performs very well. It's smooth and produces a lot of midrange power that helps the Santa Fe build speed rapidly. It's also quieter than the base four-cylinder. Still, passing power is modest with this engine, too, and the automatic transmission's unwillingness to kick down into its lower gears is partly to blame. Gas-pedal responsiveness is an issue with the turbo engine, as well; there's some lag when starting off from a stop regardless of whether you're in Comfort or Sport. Once you're moving, the gas pedal can feel a bit too responsive, with a jumpiness that makes accelerating smoothly more difficult than it should be.
The Santa Fe's suspension is comfort-oriented without feeling floaty, which seems like the right approach for this class. It feels composed and stable through sweeping corners, but handling suffers on more challenging roads due to numb, isolating steering feel and moderate body roll in tight corners.
Hyundai touts the Santa Fe's variable-density front seats, which use three types of cushioning. The seats are wide and supportive, but the cushions felt a little flat. Cloth upholstery is standard, and leather seating surfaces and heated front seats are included on Limited and higher trims.
The 60/40-split backseat is comfortable for adults. There's good legroom, and the seat cushion is high enough off the floor to provide thigh support — an attribute that's gradually vanishing across the market. On SEL Plus and higher trims, the seat slides forward and backward to balance cargo and passenger needs. The rear backrest reclines quite a bit, which gives stargazers a good view out the optional panoramic moonroof.
Materials quality in the high-end Ultimate trim is good, and the controls are sensibly arranged. The dashboard's separated sections are intuitive, with a standard 7-inch touchscreen positioned above the center vents and air-conditioning controls, but the optional dual-zone automatic air-conditioning system's temperature display is hard to read if viewed through polarized sunglasses.
Standard technology features include Bluetooth streaming audio and Apple CarPlay and Android Auto smartphone connectivity. Satellite radio, an Infinity premium stereo, a head-up display, a 360-degree camera system, wireless device charging and a larger, 8-inch touchscreen with built-in navigation are optional.
The Santa Fe has 35.9 cubic feet of cargo room behind the rear seat. The backseat folds flat with the cargo floor for a maximum 71.3 cubic feet of cargo room. There are two large bins under the cargo floor for storing items out of sight.
In Insurance Institute for Highway Safety testing, the 2019 Santa Fe received the highest rating, good, in all crash tests, and the organization rated the SUV's standard forward collision warning and automatic emergency braking systems superior, the best possible score.
Other standard active-safety features include adaptive cruise control with stop-and-go capability, blind spot warning, lane keep assist, rear cross-traffic alert and a driver-drowsiness monitor.
SEL Plus and higher trims also have Hyundai's Rear Occupant Alert system. It monitors the backseat using a sensor, and if movement is detected after the SUV has been locked, the horn honks and the Hyundai Blue Link system sends an alert to a paired smartphone. While safety technology like this is welcome, we still recommend that drivers traveling with small children place in the rear seat something they plan on taking with them at the end of the trip, like a backpack or purse, to help minimize the chances a child is accidentally left inside.
Hyundai has long been known for giving shoppers a lot for their money, and the redesigned Santa Fe reinforces that reputation with its long list of standard active-safety and technology features at a starting price thousands of dollars less than some competitors. There's a lot here to like — especially if the drivetrain quirks aren't deal-breakers for you.


text:
Emil Friedrich Knoblauch (1864-1936) est un botaniste allemand auteur de nombreuses descriptions de plantes, des traités et manuels de botanique et d'écologie.

Biographie et carrière

Publications
  Handbuch der systematischen Botanik (1890).
  Anatomie des Holzes der Laurineen, Inaugural-Dissertati (1888).
  Lehrbuch der ökologischen Pflanzen geographie Eugenius Warming et Emil Friedrich Knoblauch (1896).
  Oleaceae.
  Ökologische Anatomie der Holzpflanzen der südafrikanischen immergrünen Buschregion, Habilitationsschrift (1896)

Liens externes

Botaniste allemand du XIXe siècle
Botaniste allemand du XXe siècle
Étudiant de l'université de Königsberg
Naissance en décembre 1864
Naissance dans la province de Prusse
Décès en février 1936
Décès à Berlin
Décès à 71 ans

redpajama_set_name: RedPajamaWikipedia


Libby Squire's family joined staff and students at Hull University to remember the 21-year-old who's body was discovered in the Humber Estuary.
Tributes were read and a minute's silence was held outside the Brynmor Jones Library on the campus. The vice chancellor of the university and the president of the students union addressed the crowds.
Those who attended the event then made the short walk over to a tree at the university, where flowers for Libby were laid.
Earlier, an inquest into Libby's death was opened and the coroner Professor Paul Marks was told how the student was identified by her fingerprints. Police also confirmed they are treating her death as a homicide.
Det Supt Martin Smalley said they were still acquiring pathological and forensic evidence and so were unable to release the body back to the family for burial.
The inquest was adjourned until a future date which is yet to be confirmed.
Libby, who studied philosophy and was described as a popular student, was found dead in the Humber Estuary last Wednesday afternoon.
My baby girl is gone. Gone forever. No more birthdays with us. No more Christmas Days with us. No more family time all together.
I cannot thank you enough my darling Pie for making me a mummy. For choosing me to be your mummy. It's an honour, a privilege and a joy. I kept you safe for as long as I could and I am so sorry I could not keep you safe on that night. I'm sorry. I'm so so sorry."


GBA4ios on ios 9.2 : There are many types of emulators available which help one in running games of different consoles on iPhones and iPads and GBA4iOS is one of these emulators. Using this free emulator you will be able to play all the Gameboy Advance games on your iPad and iPhone for free.
If you are using iOS 9.2 on your iPhone or iPad you can download and GBA4iOS on your iPhone by following the guide below. You don't need to install Cydia or jailbreak your device as you just have to install an application and you are ready to play all the Gameboy Advance games on your iPhone.
Follow the step by step guide shared below which will help you to download GBA4iOS on your iPhone or iPad running on iOS 9.2 operating system.
First of all, you have to open the browser which you are using on your iPhone. Once the browser is opened, you have to open the website from where you have to download GBA4iOS.
The link which needs to be opened is http://iemulators.com/gba4ios. Alternatively, you can click on this link and you will be redirected to the GBA4iOS website.
The download page of GBA4iOS will open on your iPhone. You will see an Install button on the page. Clicking on this button will begin downloading of the emulator on your iPhone and the time to finish downloading will depend on your internet connection.
GBA4iOS will automatically get installed on your iPhone and once installed you will see it on your home screen.
Tap on the GBA4iOS button and the app should start running.
If in any case you are not able to open the app on your iPhone you need to make some changes in the settings as GBA4iOS is a third party application. Open the Settings of your iPhone and then go to General. Once you have opened General go to Device Management and select Xiamen. Tap on Trust button and go back to home screen of your iPhone. Tap on the app icon and you should be able to open GBA4iOS on your iPhone.
To download the ROM's on your iPhone all you have to do is open the app on your iPhone and tap on Search icon. Search any ROM which you want to download using the search bar and download it on your iPhone.
If you want to activate dropbox sync feature on your iPhone you can open Settings of the app. Scroll down and you will see Dropbox Sync option. The feature is turned off by default so you can enable it and give the required permissions. The game data can also be saved using Dropbox sync.
We hope that you were able to install and use GBA4iOS on your iPhone after following this guide.


On a Saturday morning, head to the Old Biscuit Mill in Woodstock for the Neighbourgoods Market, which offers fresh produce and eclectic street food. In town, the V&A Waterfront at Granger Bay hosts both the V&A Food Market and Oranjezicht City Farm market day.
On top of a silo in the Old Biscuit Mill is the Pot Luck Club, where chef Wesley Randles works a vibrant open kitchen in a room with views of Cape Town and Table Mountain (reserve, or risk the few walk-in slots). Downtown, Irishman Liam Tomlin follows the tapas-style path at Chef's Warehouse and Canteen with a menu that changes daily.
Head to colourful Bo-Kaap, home to the Cape Malay community. Try a sweet-yet-spicy curry in one of the local restaurants, then head for the Atlas Trading Company to stock up on their mother-in-law (fiery hot) and father-in-law spice mixes.
Cape Town loves its coffee and perhaps the first place to sample the bean scene is pioneering Truth Coffee, a glorious roastery and cafe in steampunk style, with vintage machines, exposed pipework and quirkily-costumed staff.
hotel on the V&A Waterfront is a complimentary tutored wine tasting, held in the bar of the Signal Restaurant by sommelier Marlvin Gwese, who offers his insights into Pinotage, Chenin Blanc and Méthode Cape Classique sparkling wines.


The idea of consuming more fruits and vegetables in our diet has never been a secret. But with our hectic schedules and demanding lives, it can be easy to forget the basics. We remind ourselves of this every day in our mantra: Get Back to Your Roots.
It reminds us to constantly move towards simplicity and away from complication. To abandon the dogmatic, regimented approach to health and wellness, and to return to this universal truth, that eating a diet with more nutrient-rich fruits and vegetables is always a good thing. At Rootbar that is one thing you can be assured of getting!
Wellness rarely involves radical, unsustainable changes. Our belief is that life can be better every single day through small choices toward a healthier lifestyle. We've learned from experience that when you treat your body well, your mind and emotions follow suit. So many of the elements of life begin to fall into place when we give our bodies the care they deserve. So join the Rootbar, and get back to your roots.
The benefits of detoxing are more about what you leave out than what you put in. Your body naturally performs functions that act to detoxify, maintain homeostasis and allow healing to occur. These include the daily dialysis of blood by your kidneys, which rids your body of harmful waste, the control of blood sugar levels by the pancreas and liver, the fighting of infection by the lymphatic system, regulation of acids and bases by the lungs, as well as many other important tasks.


text:
Q: How to make TypeScript type guard have an effect on compilation? I created a class called KVMap which inherits from Map, but with whole different types.
class KVMap<T extends object> extends Map<keyof T, T[keyof T]> {
    ...

Normally Maps are used between only two types, like Record, yet objects have known key to type associations, so I implemented just that, yet in a Map.
Example:
type T = {
    a: number,
    b: bigint,
    c: string
};

// becomes

type T = {
    get(key: "a"): number | undefined,
    set(key: "a", value: number): T,

    get(key: "b"): bigint | undefined,
    set(key: "b", value: bigint): T,

    get(key: "c"): string | undefined,
    set(key: "c", value: string): T,
};

All types are optionally undefined as one can call .clear or .delete on the keys.
So far everything works fine.
There was one problem with the original type for Map: calling .has meant that you could still get compiler errors.
Example:
if ( map.has(foo) ) {
    map.get(foo)() // error: object may be undefined
}

This is due to .has simply returning a boolean.
I sought to fix that.
I redefined .has in my inherited class as the following:
has<K extends keyof T>(key: K): this is this & {
    get(key: K): T[K]
};

This should mean that calling .get afterward would no-longer have | undefined in its type.
Yet I think that the original type of this, since it contains the optional undefined, is taking precedence over the type guard union.
Does anyone know how I could fix this?
(I could attach more code, should it be necessary)

A: It's not clear from the handbook documentation, but when you create an intersection of two callable types, the type it produces acts like an overloaded function with two call signatures, in the same order as they appear in the intersection. And so while intuitively intersections should be commutative and in TypeScript they usually are, intersections of function types are not:
type FN = {foo(): number};
type FS = {foo(): string};

declare const ns: FN & FS;
ns.foo().toFixed(); // okay
ns.foo().toUpperCase(); // error

declare const sn: FS & FN;
sn.foo().toFixed(); // error
sn.foo().toUpperCase(); // okay

ns.foo() returns a number, while sn.foo() returns a string, because in both cases the first call signature hides the second call signature.

So the problem with your type guard this is this & { get(key: K): T[K] } is that the original this had a get() method of type Map<keyof T, T[keyof T]>["get"], and so the resulting intersection just adds a new overloaded method after that.  Since the original get() method works for all keyof T inputs, it will always be selected, and so the overloaded method you added is completely hidden:
  interface Tee {
    a: string,
    b: number,
    c: boolean
  }

  const v = new KVMap<Tee>();

  if (v.has("a")) {
    v.get; /* OVERLOADED:
    get(key: "a" | "b" | "c"): string | number | boolean | undefined;
    get(key: "a"): string
    */

    v.get("a").toUpperCase(); // error!

Probably the easiest way to deal with this is to change the order of your intersection so that this is last.  So every time you guard with has(), a true result should add the new get() call signature to the beginning of the overload list, and thus it should take precedence:
  class KVMap<T extends object> extends Map<keyof T, T[keyof T]> {
    declare readonly has: <K extends keyof T>(key: K) => this is {
      get(key: K): T[K]
    } & this;
  }

  const v = new KVMap<Tee>();
  if (v.has("a")) {
    v.get("a").toUpperCase(); // okay now
  }

Hooray.

Please note, though, that such a type guard only makes sense if you are passing values of a single string literal type to has().  If the parameter to has() is of a union type, you will have a bad time, and you could still end up with undefined at runtime despite the compiler's assurances to the developer that it's not possible:
  // problem
  const bc = Math.random() < 0.5 ? "b" : "c";
  const cb = (bc === "b") ? "c" : "b";
  if (v.has(bc)) {
    v.get(cb).toString(); // compiles fine, but error at runtime!
  }

So be careful.

Playground link to code

redpajama_set_name: RedPajamaStackExchange


With a user data base in excess of 1.2 billion people, Facebook is by far the most popular social network in existence.
Check whether the icon has been set to hide in the notification area.
Access the hidden messages in Facebook Messenger by following our guide for Windows,.
When chatting on Facebook Messenger you come across various icons near the text message you sent to indicate the details about that particular message. We recommend people access Facebook Messages on the desktop via Facebook.com or Messenger.com. GONE.
Yet another load of photos,my mobile album has disappeared,why 2,000.Hi cranberry67, - Are you referring to the Windows Live Messenger icon. We tuned this car to 440rwkw and also tuned the auto late last year and has.On your account, click on the Messages icon located at the top of the page. 3.
If you use Facebook Messenger all day, our guide for Messenger tips and tricks should come. (it has the familiar location pin icon). 11. Use Facebook Messenger.
But after the first few squirts it was gone. twitter facebook pinterest youtube instagram. The Guardian - Back to home. Make a. Another alternative for those trying to escape the clutches of Facebook Messenger is to use the Facebook mobile website,.Why You Might Not Want to Use Facebook Messenger to Send Videos You can now use Facebook Messenger for iOS and Android to send photos and video to your Friends.Facebook video call icon is missing and unable to find the option to download it.
Emojis that previously displayed in Messenger for iOS, Android, and web.If your Messages icon on Facebook is missing from the left-hand column, then you may have removed it accidentally.
No facebook chat icon in facebook app. cant see the chat icon - message at buttom of my facebook page in the app. since Facebook Messenger is a separate app.
The next batch of Facebook symbols are well known. any new Facebook icons that you. with a gray hand that appears in facebook messenger menu when.
Also when I do log out on facebook, the messenger icon goes back to.
The ultimate Facebook Messenger tutorial. Gone are the days of needing to.Just like the general Notifications option under the gear icon of the Messenger.
As promised, the Windows 10 PC version of Facebook Messenger is now live for everyone in the Windows Store, following a closed beta test.To start a video call, tap on the new camera icon,...Visit Ducati official website. Icon. Configure Discover. Mach2.0. Mach2.0. Configure Discover.
The software is still in the phone just the icon was deleted.


Mickie Potatoes makes Jeremiah Worthington Jr. an offer he can't refuse.
Quality time pieces aren't always easy to come by. There's so much cheap junk on the black market.
I know, right? You'd think that there'd be plenty of quality time pieces on the black market.