The cavity ringdown spectrum of the visible electronic system of thiophosgene: An estimation of the lifetime of the T1(ã  3A2) triplet state

Abstract

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Insights into dynamics of the S2 state of thiophosgene from ab initio calculations

“…Electronic radiationless transitions in the Cl 2 CS molecules have been extensively investigated, [13][14][15][16] which is based on the rate theory of radiationless transition developed by Lin. 37 A transition from one electronic state to another of lower energy is subject to symmetry selection.…”

“…32,33 The S 2 potential energy surface was constructed on the basis of the complete-activespace self-consistent field ͑SCF͒ ͑CASSCF͒ calculations, experimental vibrational frequencies, and tunneling splittings. 34 As a complementary of the experimental work, Moule and co-workers 13 have carried out the MP2/6-31G(d,p) optimizations of the S 0 and T 1 equilibrium geometries of Cl 2 CS. It is obvious that only limited theoretical information is available for the excited states of Cl 2 CS.…”

“…6,7 Recent studies that involve the S 1 , T 1 , and S 0 states of Cl 2 CS focus mainly on radiationless transition among the three electronic states. [13][14][15][16] The T 1 thiophosgene decays almost exclusively by the nonradiative T 1 →S 0 intersystem crossing. However, the S 1 →S 0 internal conversion was found to be inefficient for Cl 2 CS in gas phase, 14 which is most likely due to absence of a promoting mode.…”

A refined quartic potential energy surface and large scale vibrational calculations for S0 thiophosgene

“…Thiophosgene has been recognized both as a suitable molecule for studying ''backbone'' intramolecular vibrational energy redistribution (IVR) in the ground electronic state S 0 [3,4,8,9], as well as ''a molecule, tailor-made for studying fundamental concepts of electronic radiationless transitions'' [1,2,[5][6][7]. The vibrational spectroscopy of thiophosgene has also been studied in considerable detail, although even at the present time some vibrational fundamentals have not been directly observed.…”

“…Thiophosgene is an interesting molecule, that has attracted considerable attention both experimentally as well as theoretically, as it has proved to be a very suitable model system for studying of a large variety of generic spectral and photophysical manifestations in polyatomic molecules [1][2][3][4][5][6][7][8][9][10][11][12]. Thiophosgene has been recognized both as a suitable molecule for studying ''backbone'' intramolecular vibrational energy redistribution (IVR) in the ground electronic state S 0 [3,4,8,9], as well as ''a molecule, tailor-made for studying fundamental concepts of electronic radiationless transitions'' [1,2,[5][6][7].…”