US EPA

6325303 

Journal Article 

Perfluoroalkanes: Conformational analysis and liquid-state properties from ab initio and Monte Carlo calculations 

Watkins, EK; Jorgensen, WL 

2001 

1 

Journal of Physical Chemistry A
ISSN: 1089-5639
EISSN: 1520-5215 

105 

16 

4118-4125 

English 

10.1021/jp004071w 

WOS:000168441700023 

Classical OPLS-AA force-field parameters are developed for perfluoroalkanes primarily by fitting to conformational profiles from gas-phase ab initio calculations (LMP2/cc-pVTZ(-f)//HF/6-31 G*) and to experimental data for pure liquids. The ah initio C-C-C-C profile of n-C4F10 (perfluorobutane) is similar to those from prior high-level calculations and indicates the presence of gauche (g) and ortho to) minima and of anti (a) minima slightly offset from 180 degrees. Ab initio torsional profiles for n-C5F12 (perfluoropentane) and (CF3)(2)CFCF2CF3 (perfluoro-2-methylbutane) also show three sets of energy minima. Special OPLS-AA torsional parameters for these three molecules closely match ab initio and experimental geometries, conformational energies (DeltaE(min)), and conformational energy barriers. These specialized force fields were merged to provide a generalized force field for linear, branched, and cyclic perfluoroalkanes. The resultant parameters yield key DeltaE(min) values within 0.6 kcal/mol of the ab initio results for the three test compounds but more poorly represent the energy barriers. The parametrization also included reproduction of experimental liquid properties of these compounds, CF4 (perfluoromethane) and c-C5F10 (pefluorocyclopentane) via Monte Carlo (MC) simulations. MC simulations of six additional molecules were also performed in order to test the transferability of the force field.