Physical Sciences and Mathematics Commons^™

Comparison Of Proton Transfers In (S2h5)+ And (O2h5)+, L. Bigham, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

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 …