Physically Motivated, Robust, ab Initio Force Fields for CO2 and N2

K Yu, JG McDaniel, JR Schmidt - The Journal of Physical …, 2011 - ACS Publications
The Journal of Physical Chemistry B, 2011ACS Publications
We present a novel methodology for developing physically motivated, first-principles
polarizable force fields and apply these techniques to the specific cases of CO2 and N2.
Exchange, electrostatic, induction, and dispersion interaction parameters were fit to
symmetry adapted perturbation theory (SAPT) dimer energy calculations, with explicit terms
to account for each of the dominant fundamental interactions between molecules. Each term
is represented by a physically appropriate functional form and fitted individually based on …
We present a novel methodology for developing physically motivated, first-principles polarizable force fields and apply these techniques to the specific cases of CO2 and N2. Exchange, electrostatic, induction, and dispersion interaction parameters were fit to symmetry adapted perturbation theory (SAPT) dimer energy calculations, with explicit terms to account for each of the dominant fundamental interactions between molecules. Each term is represented by a physically appropriate functional form and fitted individually based on the results of the SAPT decomposition. The resulting CO2 and N2 force field was benchmarked against a diverse set of experimental data, including the second virial coefficient, density, scattering structure factor, heat capacity, enthalpy of vaporization, and vapor–liquid coexistence curves. In general, excellent agreement with experimental data is obtained with our model. Due to the physical nature of their construction, these force fields are robust and transferable to environments for which they were not specifically parametrized, including gas mixtures, and we anticipate applications in modeling CO2/N2 adsorption in polar and/or heterogeneous media.
ACS Publications
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