TY - JOUR
T1 - Vibrationally resolved emission of thiophosgene dimer
AU - Berrios, Eduardo
AU - Hui, Ho Yee
AU - Gruebele, Martin
N1 - Funding Information:
This work was supported by a grant from the National Science Foundation , CHE 1012075 and in part by the National Science Foundation through TeraGrid resources provided by NCSA under grant number TG-CHE090133 . E.B. was supported by a Fulbright-CONICYT Fellowship. H.Y.H. was supported by summer undergraduate research funding from the NSF.
PY - 2010/9/20
Y1 - 2010/9/20
N2 - During a study of thiophosgene electronic spectra, Fujiwara and co-workers observed a broad electronic transition peaked at 37 000 cm-1, attributed to thiophosgene dimer. Our dispersed fluorescence spectra of a thiophosgene molecular beam excited at 36 000 cm-1 reveal several vibrational modes too low in frequency for thiophosgene. We assign them to modes of thiophosgene dimer or their combination bands. MP2 calculations support the vibrational assignment. TD-DFT, CASSCF, and coupled cluster calculations suggest that the bright electronic state of thiophosgene dimer is the B2u symmetry fifth excited singlet state. Two additional transitions are assigned to a thiophosgene synthesis impurity, trichloromethanesulfenyl chloride.
AB - During a study of thiophosgene electronic spectra, Fujiwara and co-workers observed a broad electronic transition peaked at 37 000 cm-1, attributed to thiophosgene dimer. Our dispersed fluorescence spectra of a thiophosgene molecular beam excited at 36 000 cm-1 reveal several vibrational modes too low in frequency for thiophosgene. We assign them to modes of thiophosgene dimer or their combination bands. MP2 calculations support the vibrational assignment. TD-DFT, CASSCF, and coupled cluster calculations suggest that the bright electronic state of thiophosgene dimer is the B2u symmetry fifth excited singlet state. Two additional transitions are assigned to a thiophosgene synthesis impurity, trichloromethanesulfenyl chloride.
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U2 - 10.1016/j.cplett.2010.08.014
DO - 10.1016/j.cplett.2010.08.014
M3 - Article
AN - SCOPUS:77956494583
VL - 497
SP - 163
EP - 167
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 4-6
ER -