On the role of charge transfer in the stabilization of weakly bound complexes involving water and hydrogen sulphide molecules

A charge-displacement analysis allows to quantitatively assess charge-transfer effects in hydrogen-bonded complexes. [Display omitted] ► We compare water with hydrogen sulphide both interacting with krypton. ► In both cases the interaction possesses a definite charge transfer component. ► Charge-tra...

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Bibliographic Details
Published in:Chemical physics 2012-04, Vol.398, p.176-185
Main Authors: Pirani, F., Candori, P., Pedrosa Mundim, M.S., Belpassi, L., Tarantelli, F., Cappelletti, D.
Format: Article
Language:English
Subjects:
Charge transfer
Hydrogen bond
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Summary:A charge-displacement analysis allows to quantitatively assess charge-transfer effects in hydrogen-bonded complexes. [Display omitted] ► We compare water with hydrogen sulphide both interacting with krypton. ► In both cases the interaction possesses a definite charge transfer component. ► Charge-transfer differs slightly in the two systems and exhibits different stereoselectivity. Integral cross section data for collisions of water and hydrogen sulphide molecules with noble gas atoms, measured with the same apparatus under identical conditions and analyzed by exploiting the same potential model, provided a set of internally consistent potential parameters. Their critical comparison is exploited not only to identify those systems where the intermolecular bond is not simply due to the balancing of size repulsion with dispersion and induction attraction, but also to establish the amount of bond stabilization by charge-transfer effects. Such experimental findings are analyzed through extensive and accurate ab initio calculations, addressed at discovering the relevant differences in the basic features of the potential energy surfaces. In particular, we have analyzed in detail the prototype H2S, H2O–Kr systems and found pronounced differences in the dependence of the interaction nature and energy on the relative orientation of the colliding systems. Using the recently proposed charge-displacement analysis we have been able to quantitatively assess charge-transfer effects, which differ significantly in the two systems and exhibit different stereoselectivity. This casts further light on the specificity of water interactions.
ISSN:0301-0104
DOI:10.1016/j.chemphys.2011.03.030