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Ab initio molecular dynamics of liquid hydrogen chloride
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10.1063/1.1869972
/content/aip/journal/jcp/122/11/10.1063/1.1869972
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/11/10.1063/1.1869972

Figures

Image of FIG. 1.
FIG. 1.

Equilibrium structure of symmetry obtained for the dimer within our ab initio scheme.

Image of FIG. 2.
FIG. 2.

Evolution of (a) the Kohn–Sham (KS) energy, (b) the fictitious electronic kinetic energy , and (c) the temperature during the ab initio molecular dynamics simulation. The figures in (a) correspond to the difference between the instantaneous Kohn–Sham energy and the Born–Oppenheimer surface.

Image of FIG. 3.
FIG. 3.

Electronic density of states (DOS) of liquid HCl, derived from both Car–Parrinello (dashed) and fully relaxed eigenvalues (solid). The energy levels are referenced with respect to the average highest occupied molecular orbital level and were broadened with a Gaussian function of width of . The vertical lines give the calculated eigenvalues for the isolated HCl molecule.

Image of FIG. 4.
FIG. 4.

Total neutron structure factor of liquid HCl as obtained from the (a) classical and (b) ab initio simulations. The calculated structure factors (dashed) are compared to the experimental one obtained by neutron diffraction (solid) (Ref. 3).

Image of FIG. 5.
FIG. 5.

Partial structure factors of liquid HCl as obtained from the classical simulation (dashed) and from neutron diffraction experiments (solid) (Ref. 3): (a) Cl–Cl, (b) Cl–H, and (c) H–H.

Image of FIG. 6.
FIG. 6.

Partial structure factor of liquid HCl as obtained from the ab initio simulation (dashed) and from neutron diffraction experiments (solid) (Ref. 3): (a) Cl–Cl, (b) Cl–H, and (c) H–H.

Image of FIG. 7.
FIG. 7.

Radial distribution functions as obtained from the classical simulation (dashed) and from neutron diffraction experiments (solid) (Ref. 3): (a) Cl–Cl, (b) Cl–H, and (c) H–H.

Image of FIG. 8.
FIG. 8.

Radial distribution functions as obtained from the ab initio simulation (dashed) and from neutron diffraction experiments (solid) (Ref. 3): (a) Cl–Cl, (b) Cl–H, and (c) H–H.

Image of FIG. 9.
FIG. 9.

Distribution of intramolecular Cl–H distances as obtained from the ab initio simulation (solid). The calculated equilibrium distance of the isolated HCl molecule is indicated by a vertical dashed line.

Image of FIG. 10.
FIG. 10.

Probability that a donor H (solid) or an acceptor Cl (dashed) forms 0 (circles), 1 (disks), or 2 (squares) hydrogen bonds as a function of the hydrogen-bond bond length , as obtained from the ab initio simulation.

Image of FIG. 11.
FIG. 11.

Probability of finding a molecule in a hydrogen-bonded chain of length , as obtained from the ab initio simulation.

Image of FIG. 12.
FIG. 12.

Probability distribution of finding two molecules with centers of mass separated by a distance and with relative orientations described by the angle defined in Fig. 1, as obtained from the ab initio simulation.

Image of FIG. 13.
FIG. 13.

Probability distribution of finding two molecules with centers of mass separated by a distance and with relative orientations described by the angle defined in Fig. 1, as obtained from the ab initio simulation. Only molecules with were retained in this analysis.

Image of FIG. 14.
FIG. 14.

Probability distribution of finding two neighboring molecules with relative orientations described by angles and defined in Fig. 1, as obtained from the ab initio simulation. Only molecules with centers of mass separated by a distance ranging between 3 and 4 Å were retained in this analysis.

Image of FIG. 15.
FIG. 15.

Partial structure factor of liquid HCl as obtained from an ab initio simulation with the BLYP exchange-correlation functional (dashed) and from neutron diffraction experiments (solid) (Ref. 3): (a) Cl–Cl, (b) Cl–H, and (c) H–H.

Image of FIG. 16.
FIG. 16.

(a) Evolution of the mean square displacement (MSD) of Cl atoms in -HCl. (b) Evolution of the velocity-velocity correlation function. The inset corresponds to the diffusion coefficient obtained using Eq. (8).

Image of FIG. 17.
FIG. 17.

Orientational time correlation function for a vector fixed along the molecular axis of HCl. The result (solid) corresponds to an average over all the molecules and over time in the ab initio simulation. The exponential function (dotted) is obtained from a fit and is characterized by a decay time of .

Image of FIG. 18.
FIG. 18.

(a) Vibrational density of states (v-DOS) associated to motions of Cl (thin, solid) and H atoms (thick, solid). (b) Same as in (a) but focusing on the low-frequency bands (up to ). Also shown in (b) are the v-DOS associated to the motions of the centers of mass (thin, dotted) and to the atomic motions relative to the centers of mass (thick, dotted). The latter two curves are barely distinguishable from the v-DOS associated to Cl and H atoms, respectively.

Image of FIG. 19.
FIG. 19.

Vectorial dynamical dipole in -HCl: (a) Distribution of the dipole moment (solid), of the component along the molecular axis (dashed), and of the components along or (dotted); (b) distribution of the polar angle of the dipole with respect to the axis.

Image of FIG. 20.
FIG. 20.

Instantaneous dielectric constant as a function of the time elapsed since the onset of the electric field within (a) a simplified scheme in which the polarization is given as a sum of fixed dipoles aligned to the axes of the individual molecules and (b) the ab initio theory for the polarization. The curves correspond to an average over the same six ab initio trajectories of 3 ps.

Tables

Generic image for table
Table I.

Properties of the HCl monomer calculated within our ab initio scheme: equilibrium distance , binding energy , vibrational frequency , and dipole moment . Our results are compared with experimental data (Refs. 31, 41, and 42) and with results from configuration interaction (CI) (Ref. 45) and averaged coupled pair functional (ACPF) (Ref. 46) calculations.

Generic image for table
Table II.

Structural parameters (, , and ) and binding energy corresponding to the equilibrium structure of symmetry found for the dimer within our ab initio scheme. The angles and are defined in Fig. 1. Our results are compared with experimental data (Refs. 43 and 44) and with results from ACPF (Ref. 46) calculations.

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/content/aip/journal/jcp/122/11/10.1063/1.1869972
2005-03-23
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ab initio molecular dynamics of liquid hydrogen chloride
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/11/10.1063/1.1869972
10.1063/1.1869972
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