TY - JOUR
T1 - The hypothiocyanite radical OSCN and its isomers
AU - Wu, Zhuang
AU - Xu, Jian
AU - Liu, Qifan
AU - Dong, Xuelin
AU - Li, Dingqing
AU - Holzmann, Nicole
AU - Frenking, Gernot
AU - Trabelsi, Tarek
AU - Francisco, Joseph S.
AU - Zeng, Xiaoqing
N1 - Publisher Copyright:
© the Owner Societies 2017.
PY - 2017
Y1 - 2017
N2 - A biologically relevant reactive sulfur species (RSS), the hypothiocyanite radical OSCN, is generated in the gas phase through flash vacuum pyrolysis (FVP) of trifluoromethyl sulfinyl cyanide CF3S(O)CN at ca. 1000 K. Upon UV light irradiation (365 nm), OSCN rearranges to novel isomers OSNC and SOCN, and further visible light irradiation (400 ± 20 nm) leads to reverse isomerization. The identification of OSCN, OSNC, and SOCN in cryogenic matrices (Ar and N2, 2.8 K) with IR spectroscopy is supported by quantum chemical calculations up to the CCSD(T)-F12/VTZ-F12 level. The potential energy surface for the interconversion of OSCN isomers and their bonding properties are computationally explored by using the CCSD(T)-F12/VTZ-F12 and EDA-NOCV methods, respectively.
AB - A biologically relevant reactive sulfur species (RSS), the hypothiocyanite radical OSCN, is generated in the gas phase through flash vacuum pyrolysis (FVP) of trifluoromethyl sulfinyl cyanide CF3S(O)CN at ca. 1000 K. Upon UV light irradiation (365 nm), OSCN rearranges to novel isomers OSNC and SOCN, and further visible light irradiation (400 ± 20 nm) leads to reverse isomerization. The identification of OSCN, OSNC, and SOCN in cryogenic matrices (Ar and N2, 2.8 K) with IR spectroscopy is supported by quantum chemical calculations up to the CCSD(T)-F12/VTZ-F12 level. The potential energy surface for the interconversion of OSCN isomers and their bonding properties are computationally explored by using the CCSD(T)-F12/VTZ-F12 and EDA-NOCV methods, respectively.
UR - http://www.scopus.com/inward/record.url?scp=85024114951&partnerID=8YFLogxK
U2 - 10.1039/c7cp02774e
DO - 10.1039/c7cp02774e
M3 - 文章
C2 - 28621378
AN - SCOPUS:85024114951
SN - 1463-9076
VL - 19
SP - 16713
EP - 16720
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 25
ER -