Premium
Viabilty of atomistic potentials for thermodynamic properties of carbon dioxide at low temperatures
Author(s) -
Kuznetsova Tatyana,
Kvamme Bjørn
Publication year - 2001
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.1130
Subject(s) - thermodynamics , chemistry , enthalpy of vaporization , parametrization (atmospheric modeling) , supercritical fluid , polynomial , vapor pressure , enthalpy , thermodynamic integration , potential energy , computational chemistry , molecular dynamics , physics , atomic physics , mathematical analysis , mathematics , quantum mechanics , radiative transfer
Abstract Investigation into volumetric and energetic properties of several atomistic models mimicking carbon dioxide geometry and quadrupole momentum covered the liquid–vapor coexistence curve. Thermodynamic integration over a polynomial and an exponential‐polynomial path was used to calculate free energy. Computational results showed that model using GROMOS Lennard–Jones parameters was unsuitable for bulk CO 2 simulations. On the other hand, model with potential fitted to reproduce only correct density–pressure relationship in the supercritical region proved to yield correct enthalpy of vaporization and free energy of liquid CO 2 in the low‐temperature region. Except for molar volume at the upper part of the vapor–liquid equilibrium line, the bulk properties of exp‐6‐1 parametrization of ab initio CO 2 potential were in a close agreement with the experimental results. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1772–1781, 2001