Premium
Thermodynamics of hydrogen bonding from molecular orbital theory: 1. Water
Author(s) -
Wolbach Jeffrey P.,
Sandler Stanley I.
Publication year - 1997
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690430622
Subject(s) - thermodynamics , hydrogen bond , ab initio , enthalpy , chemistry , density functional theory , statistical physics , hydrogen , molecular orbital , entropy (arrow of time) , computational chemistry , molecule , physics , organic chemistry
To reduce the number of adjustable parameters that appear in the thermodynamic modeling of hydrogen‐bonding fluids, the use of ab‐initio molecular orbital calculations in the form of Hartree–Fock and density functional theories to compute thermodynamic properties are considered. In particular, the enthalpy and entropy changes on hydrogen bonding for water are computed. The theory, the computational methods and the basis sets used, as well as the results for water, are discussed. The results obtained are compared with those of others and with experimental estimates from the literature to determine the validity of the methods that are then used in this extended study. The results obtained here are also used to examine the validity of mixture group contribution results obtained here are also used to examine the validity of mixture group contribution methods for hydrogen‐bonding mixtures, to develop simple estimation procedures for model parameters, and to reduce the number of calculations such as those as those described that need to be done.