dorsal/arxiv
View SchemaFrom ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia
| Authors | A. Daniel Boese, Amalendu Chandra, Jan M. L. Martin, Dominik Marx |
|---|---|
| Categories | |
| ArXiv ID | physics/0306154 |
| URL | https://arxiv.org/abs/physics/0306154 |
| DOI | 10.1063/1.1599338 |
| Journal | Journal of Chemical Physics 119, 5965 - 5980 (2003) |
Abstract
The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liquid ammonia to judge its performance in describing the associated liquid. Both the HCTH/407+ and BLYP functionals describe the properties of the liquid well as judged by analysis of radial distribution functions, hydrogen bonding structure and dynamics, translational diffusion, and orientational relaxation processes. It is demonstrated that the solvation shell of the ammonia molecule in the liquid phase is dominated by steric packing effects and not so much by directional hydrogen bonding interactions. In addition, the propensity of ammonia molecules to form bifurcated and multifurcated hydrogen bonds in the liquid phase is found to be negligibly small.
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"abstract": "The ammonia dimer (NH3)2 has been investigated using high--level ab initio\nquantum chemistry methods and density functional theory (DFT). The structure\nand energetics of important isomers is obtained to unprecedented accuracy\nwithout resorting to experiment. The global minimum of eclipsed C_s symmetry is\ncharacterized by a significantly bent hydrogen bond which deviates from\nlinearity by about 20 degrees. In addition, the so-called cyclic C_{2h}\nstructure is extremely close in energy on an overall flat potential energy\nsurface. It is demonstrated that none of the currently available (GGA,\nmeta--GGA, and hybrid) density functionals satisfactorily describe the\nstructure and relative energies of this nonlinear hydrogen bond. We present a\nnovel density functional, HCTH/407+, designed to describe this sort of hydrogen\nbond quantitatively on the level of the dimer, contrary to e.g. the widely used\nBLYP functional. This improved functional is employed in Car-Parrinello ab\ninitio molecular dynamics simulations of liquid ammonia to judge its\nperformance in describing the associated liquid. Both the HCTH/407+ and BLYP\nfunctionals describe the properties of the liquid well as judged by analysis of\nradial distribution functions, hydrogen bonding structure and dynamics,\ntranslational diffusion, and orientational relaxation processes. It is\ndemonstrated that the solvation shell of the ammonia molecule in the liquid\nphase is dominated by steric packing effects and not so much by directional\nhydrogen bonding interactions. In addition, the propensity of ammonia molecules\nto form bifurcated and multifurcated hydrogen bonds in the liquid phase is\nfound to be negligibly small.",
"arxiv_id": "physics/0306154",
"authors": [
"A. Daniel Boese",
"Amalendu Chandra",
"Jan M. L. Martin",
"Dominik Marx"
],
"categories": [
"physics.chem-ph",
"physics.atm-clus",
"physics.comp-ph",
"physics.flu-dyn"
],
"doi": "10.1063/1.1599338",
"journal_ref": "Journal of Chemical Physics 119, 5965 - 5980 (2003)",
"title": "From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia",
"url": "https://arxiv.org/abs/physics/0306154"
},
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