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Title: New Theoretical Insight into the Interactions and Properties of Formic Acid: Development of a Quantum-Based Pair Potential for Formic Acid.

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2052707· OSTI ID:881886
; ; ;

We performed ab initio quantum chemical studies for the development of intra and intermolecular interaction potentials for formic acid for use in molecular dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter-molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
W-7405-ENG-48
OSTI ID:
881886
Report Number(s):
UCRL-JRNL-214472; JCPSA6; TRN: US200613%%174
Journal Information:
Journal of Chemical Physics, Vol. 123; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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  • Harmony, Marlin D.; Laurie, Victor W.; Kuczkowski, Robert L.
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08 HYDROGEN
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
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DEGREES OF FREEDOM
ELECTRON CORRELATION
FORMIC ACID
HYDROGEN
HYDROSTATICS
ISOMERS
MELTING
MOLECULAR CRYSTALS
MONOMERS
TRANSFORMATIONS