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Estimates of the ab Initio Limit for Sulfur−π Interactions: The H2S−Benzene Dimer
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Section:Abstract
The interaction between aromatic rings and sulfur atoms in the side chains of amino acids is a factor in the formation and stabilization of α-helices in proteins. We studied the H2S−benzene dimer as the simplest possible prototype of sulfur−π interactions. High-quality potential energy curves were obtained using coupled-cluster theory with single, double, and perturbative triple substitutions (CCSD(T)) and a large, augmented quadruple-ζ basis set (aug-cc-pVQZ). The equilibrium intermonomer distance for the hydrogens-down C2v configuration is 3.8 Å with an interaction energy of −2.74 kcal mol-1. Extrapolating the binding energy to the complete basis set limit gives −2.81 kcal mol-1. This binding energy is comparable to that of H2O−benzene or of the benzene dimer, and the equilibrium distance is in close agreement with experiment. Other orientations of the dimer were also considered at less complete levels of theory. A considerable reduction in binding for the sulfur-down configuration, together with an energy decomposition analysis, indicates that the attraction in H2S−benzene is best thought of as arising from a favorable electrostatic interaction between partially positive hydrogens in H2S with the negatively charged π-cloud of the benzene.
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This article has been cited by 14 ACS Journal articles (5 most recent appear below).
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Sulfur, Not Too Far Behind O, N, and C: SH···π Hydrogen Bond
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Himansu S. Biswal and Sanjay WategaonkarThe Journal of Physical Chemistry A2009 113 (46), 12774-12782We report hydrogen-bonded complexes of H2S with indole and 3-methyl indole stabilized by the S−H···π interaction. It is interesting to discover that although sulfur and its hydrides are known as poor hydrogen-bond donor/acceptors, sulfur is not too far ...
An Assessment of Theoretical Methods for Nonbonded Interactions: Comparison to Complete Basis Set Limit Coupled-Cluster Potential Energy Curves for the Benzene Dimer, the Methane Dimer, Benzene−Methane, and Benzene−H2S
C. David Sherrill, Tait Takatani and Edward G. HohensteinThe Journal of Physical Chemistry A2009 113 (38), 10146-10159An Assessment of Theoretical Methods for Nonbonded Interactions: Comparison to Complete Basis Set Limit Coupled-Cluster Potential Energy Curves for the Benzene Dimer, the Methane Dimer, Benzene−Methane, and Benzene−H2S
C. David Sherrill, Tait Takatani and Edward G. HohensteinThe Journal of Physical Chemistry A2009 113 (38), 10146-10159Large, correlation-consistent basis sets have been used to very closely approximate the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] complete basis set potential energy curves of several prototype nonbonded complexes, the sandwich, ...
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History
- Published In Issue January 13, 2005
- Received July 20, 2004
Revised September 30, 2004
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