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Range and strength of intermolecular forces for van der Waals complexes of the type H 2 X n ‐Rg, with X = O, S and n = 1,2
Author(s) -
Barreto Patrícia R. P.,
Palazzetti F.,
Grossi G.,
Lombardi A.,
Maciel G. S.,
Vilela A. F. A.
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.22127
Subject(s) - van der waals force , van der waals radius , chemistry , london dispersion force , intermolecular force , van der waals surface , van der waals strain , dipole , atomic physics , isotropy , van der waals molecule , theorem of corresponding states , thermodynamics , physics , molecule , quantum mechanics , organic chemistry
This study is intended as a continuation of previous experimental and theoretical works on the systems H 2 O‐Rg, H 2 S‐Rg, H 2 O 2 ‐Rg, and H 2 S 2 ‐Rg, where Rg = He, Ne, Ar, Kr, Xe. For the H 2 O‐Rg and H 2 S‐Rg systems, molecular and atomic polarizabilities have been calculated and from them, using phenomenological correlation formulas modeling the dispersion‐repulsion (van der Waals) forces, the isotropic interaction parameters have been determined and compared with experimental data from this laboratory. For the H 2 O 2 ‐Rg and H 2 S 2 ‐Rg systems, the molecular polarizabilities have been calculated and used in correlation formulas to predict well depths and positions of van der Waals forces and a comparison made with the corresponding potential energy surfaces calculated in previous works. The approach correctly predicts the interaction parameters, except for H 2 O and H 2 O 2 with the heavier rare gases. The correlation formulas have been then extended to include an attractive induction contribution accounting for the interaction between the permanent molecular dipole moment and the instantaneous induced atomic dipole moment, to improve the predicted parameters for H 2 O and H 2 O 2 ‐Ar, Kr and Xe. The agreement with experimental and theoretical data is improved but the predicted data still underestimate the interaction. This is probably due to the presence of a significant non van der Waals contribution to the interaction for the heavier gases, as suggested by analogy with the previously studied water‐Rg case. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010