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Ab initio molecular orbital calculations on hydrogen bonding in binary water‐alcohol mixtures: (CH 3 OH) 2 (H 2 O), (CH 3 OH) (H 2 O) 2 , and (CF 3 CH 2 OH)(H 2 O)
Author(s) -
Curtiss L. A.,
Frurip D. J.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560200820
Subject(s) - water dimer , dimer , chemistry , ab initio , hydrogen bond , molecular orbital , methanol , binding energy , ab initio quantum chemistry methods , computational chemistry , basis set , hydrogen , molecular dynamics , crystallography , molecule , density functional theory , atomic physics , organic chemistry , physics
Ab initio LCAO‐SCF molecular orbital calculations have been performed on open‐chain and cyclic trimers containing methanol and water and on dimers containing 2,2,2‐trifluoroethanoI and water. These calculations were done in conjunction with experimental studies of molecular association in vapors of binary mixtures. Equilibrium structures and energies were determined using the minimal STO‐3G basis set. The 2:1 and 1:2 methanol‐water cyclic trimers have similar binding energies and are more stable than their respective open‐chain trimers. Limited calculations were carried out to assess the importance of polarization functions and correlation energy in the methanol‐water trimers. These calculations confirmed the STO‐3G predictions. The most stable trifluoroethanol‐water dimer has an O—H ⃛O and an H ⃛F hydrogen bond. It has a larger interaction energy than either a trifluoroethanol dimer or a water dimer.