Computer Simulation of Trifluoromethane Properties with Ab Initio Force Field

作者：Chung Yi Hsing; Li Arvin Huang Te; Chao Sheng D^*

来源：Journal of Computational Chemistry, 2011, 32(11): 2414-2421.

DOI：10.1002/jcc.21823

• molecular dynamics simulation
• carbon trifluoride (trifluoromethane)
• ab initio force field
• radial distribution function
• self-diffusion coefficient
• velocity autocorrelation function

Intermolecular interaction potentials of the trifluoromethane dimer in 15 orientations have been calculated using the Hartree-Fock (HF) self-consistent theory and the second-order Moller-Plesset (MP2) perturbation theory. Single point energies at important geometries were also calibrated by the coupled cluster with single and double and perturbative triple excitation [CCSD(T)] calculations. We have employed Pople's medium size basis sets [up to 6-311++G(3df,3pd)] and Dunning's correlation consistent basis sets (up to aug-cc-pVQZ). Basis set limit potential values were obtained through well-studied extrapolation methods. The calculated MP2 potential data were employed to parameterize a 5-site force field for molecular simulations. We performed molecular dynamics simulations using the constructed ab initio force field and compared the simulation results with experiments. Quantitative agreements for the atom-wise radial distribution functions and the self-diffusion coefficients over a wide range of experimental conditions can be obtained, thus validating the ab initio force field without using experimental data a priori.

• 出版日期2011-8