Comparison of proton transfers in (S2H5)+ and (O2H5)+

Authors

L. Bigham
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Journal of Chemical Physics

Publication Date

1985

Volume

82

First Page

3316

Last Page

3321

Abstract

The energetics and electronic rearrangements associated with proton transfer between S atoms in (H₂S–H–SH₂)⁺ are calculated using ab initio molecular orbital methods and compared with similar data in the first‐row analog (H₂O–H–OH₂)⁺. The full potential energy surface of (S₂H₅)⁺, calculated as a function of the H‐bond length as well as the position of the proton, contains two equivalent minima separated by a small energy barrier, whereas the surface of (O₂H₅)⁺ contains a single minimum corresponding to a symmetric position for the central proton. In both cases the energy barrier to transfer increases as the H bond is lengthened. This rise is noticeably less steep in the case of (S₂H₅)⁺, a fact attributed to the greater ease with which a proton may be pulled a given distance from each SH₂ subunit in the absence of the other. Enlargements of the proton transfer barriers also result from angular distortions of each H bond; these increases are qualitatively quite similar in the two systems. There is a great deal of resemblance also in the electronic redistribution patterns accompanying proton transfer in the two systems. However, the greater polarizability of SH₂ as compared to OH₂ leads to greater overall charge transfer between the subunits in (H₂S–H–SH₂)⁺ and to larger extent of spatial regions of density change.

Comments

Originally published by American Institute of Physics in the Journal of Chemical Physics.

Publisher's PDF can be accessed through the remote link.

Recommended Citation

Comparison of proton transfers in (S[sub 2]H[sub 5])[sup + ] and (O[sub 2]H[sub 5])[sup + ] Steve Scheiner and Larry D. Bigham, J. Chem. Phys. 82, 3316 (1985), DOI:10.1063/1.448230