TY - JOUR
T1 - Spectral Characterization of Three-Electron Two-Center (3e-2c) Bonds of Gaseous CH3S-S(H)CH3 and (CH3SH)2+ and Enhancement of the 3e-2c Bond upon Protonation
AU - Xie, Min
AU - Shen, Zhitao
AU - Wang, Dandan
AU - Fujii, Asuka
AU - Lee, Yuan Pern
N1 - Funding Information:
This work was supported by the Ministry of Science and Technology, Taiwan (Grant No. MOST106-2745-M009-001-ASP and MOST107-3017-F009-003) and the Center for Emergent Functional Matter Science of National Chiao Tung University from The Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) in Taiwan. The National Center for High-Performance Computation provided computer time.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/7/5
Y1 - 2018/7/5
N2 - The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol-1.
AB - The three-electron two-center (3e-2c) bond plays an important role in structures and electron communication in biological systems involving cationic sulfur compounds. Although the nature of 3e-2c bonds and their theoretical formalism have attracted great interest, direct spectral identifications of 3e-2c-bound molecules are scarce. We observed the infrared spectra of the weakly 3e-2c-bound CH3S-S(H)CH3 and the strongly 3e-2c-bound (CH3SH)2+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet photoionization and time-of-flight detection. Protonation of CH3S-S(H)CH3 to form [CH3(H)S-S(H)CH3]+ significantly enhances the 3e-2c bond, characterized by a large red shift of the SH-stretching band with enhanced IR intensity, shortening of the calculated S-S distance from 3.00 to 2.86 Å, and a dissociation energy increased from ∼23 to 162 kJ mol-1.
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U2 - 10.1021/acs.jpclett.8b01491
DO - 10.1021/acs.jpclett.8b01491
M3 - Article
C2 - 29920092
AN - SCOPUS:85048855131
SN - 1948-7185
VL - 9
SP - 3725
EP - 3730
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 13
ER -