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Quantum‐mechanical and statistical mechanical studies of the torsional barrier of H 2 O 2 in aqueous solution
Author(s) -
Jönsson B.,
Romano S.,
Karlström G.
Publication year - 1984
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.560250306
Subject(s) - aqueous solution , monte carlo method , molecule , chemistry , quantum monte carlo , molecular dynamics , quantum , computational chemistry , force field (fiction) , thermodynamics , chemical physics , physics , quantum mechanics , organic chemistry , statistics , mathematics
Monte Carlo simulations were carried out on clusters consisting of one hydrogen peroxide molecule and n water molecules, n being 100 and 250. Quantum‐chemical potentials were used for the interactions between the species. The torsional angle was allowed to change in the simulation and its equilibrium value was found to change from ∼115° in the dilute vapor phase to ∼80° in the aqueous surrounding. At the same time the cis barrier became smaller than the trans barrier, as opposed to in the isolated molecule. A continuum model using the reaction field technique was investigated parallel with the simulations; with a reasonable size of the spherical cavity, containing the H 2 O 2 molecule, it was found possible to qualitatively reproduce the Monte Carlo results.