An improved intermolecular potential function for simulations of liquid hydrogen fluoride

Section: A Interaction Potential and Simulation Setupmentioning

confidence: 99%

Adsorption of HF and HCl molecules on ice at 190 and 235 K from molecular dynamics simulations: Free energy profiles and residence times

Toubin

Picaud

Hoang

et al. 2003

“…24 Both groups employed three-site models in their studies, but did not make use of condensed phase experimental data in their parameterizations. In 1984, Cournoyer and Jorgensen introduced the three-site TIPS model for liquid HF, 25 which greatly improved the accuracy of computed thermodynamic properties of the liquid state as compared to experiment. [3][4][5] The following year, the first neutron diffraction study of deuterium fluoride (DF) was published, 6 providing structural information, including radial distribution functions at 293 K. A direct comparison to predictions from the TIPS model was provided in that study, showing TIPS to be surprisingly accurate at 293 K.…”

Section: Introductionmentioning

confidence: 99%

Quantum mechanical force field for hydrogen fluoride with explicit electronic polarization

Mazack

Gao

2014

The explicit polarization (X-Pol) theory is a fragment-based quantum chemical method that explicitly models the internal electronic polarization and intermolecular interactions of a chemical system. X-Pol theory provides a framework to construct a quantum mechanical force field, which we have extended to liquid hydrogen fluoride (HF) in this work. The parameterization, called XPHF, is built upon the same formalism introduced for the XP3P model of liquid water, which is based on the polarized molecular orbital (PMO) semiempirical quantum chemistry method and the dipole-preserving polarization consistent point charge model. We introduce a fluorine parameter set for PMO, and find good agreement for various gas-phase results of small HF clusters compared to experiments and ab initio calculations at the M06-2X/MG3S level of theory. In addition, the XPHF model shows reasonable agreement with experiments for a variety of structural and thermodynamic properties in the liquid state, including radial distribution functions, interaction energies, diffusion coefficients, and densities at various state points.

“…[21][22][23][24] On the theoretical side, the dimer has also been studied in a variety of ways, using quantum Monte Carlo methods, [25][26][27] four-dimensional rigid rotor 28 -31 and full six-dimensional ͑6D͒ bound state calculations, [32][33][34][35][36][37] as well as vibrational predissociation calculations. 33,[37][38][39] In the theoretical work, several potential energy surfaces ͑PESs͒ have been used, 25,[40][41][42] 43 which is based on explicitly correlated second-order Møller-Plesset calculations, and which is adjusted to reproduce the experimental dissociation energy and monomer stretch frequencies. This potential has been used to describe the dimer interactions in He n (HF) 2 clusters 44 and the HF trimer, 45 but so far no rigorous test of this potential for the dimer proper has been published.…”

Section: Introductionmentioning

confidence: 99%

Spectrum and vibrational predissociation of the HF dimer. I. Bound and quasibound states

Vissers

Groenenboom

Avoird

2003

We present full six-dimensional calculations of the bound states of the HF dimer for total angular momentum Jϭ0,1 and of the quasibound states for Jϭ0 that correspond with vibrational excitation of one of the HF monomers, either the donor or the acceptor in the hydrogen bond. Transition frequencies and rotational constants were calculated for all four molecular symmetry blocks. A contracted discrete variable representation basis was used for the dimer and monomer stretch coordinates R,r A ,r B ; the generation of the monomer basis in the dimer potential leads to significantly better convergence of the energies. We employed two different potential energy surfaces: the SQSBDE potential of Quack and Suhm and the SO-3 potential of Klopper, Quack, and Suhm. The frequencies calculated with the SO-3 potential agree very well with experimental data and are significantly better than those from the SQSBDE potential.