In this work, we report on the spectroscopy and dynamics of the quasi-linear S2 state of chlorocarbene, CHCl, and its deuterated isotopologue using optical-optical double resonance (OODR) spectroscopy through selected rovibronic levels of the S1 state. This study, which represents the first observation of the S2 state in CHCl, builds upon our recent examination of the corresponding state in CHF, where pronounced mode specificity was observed in the dynamics, with predissociation rates larger for levels containing bending excitation. In the present work, a total of 14 S2 state vibrational levels with angular momentum 1 were observed for CHCl, and 34 levels for CDCl. The range of in this case was restricted by the pronounced Renner-Teller effect in the low-lying S1 levels, which severely reduces the fluorescence lifetime for levels with Ka > 0. Nonetheless, by exploiting different intermediate S1 levels, we observed progressions involving all three fundamental vibrations. For levels with long predissociation lifetimes, rotational constants were determined by measuring spectra through different intermediate J levels of the S1 state. Plots of the predissociation linewidth (lifetime) vs. energy for various S2 levels show an abrupt onset, which lies near the calculated threshold for elimination to form C(3P) HCl on the triplet surface. Our experimental results are compared with a series of high level ab initio calculations, which included the use of a dynamically weighted full-valence CASSCF procedure, focusing maximum weight on the state of interest (the singlet and triplet states were computed separately). This was used as the reference for subsequent Davidson-corrected MRCI(Q) calculations. These calculations reveal the presence of multiple conical intersections in the singlet manifold.
C. Tao et al., "Spectroscopy and Dynamics of the Predissociated, Quasi-Linear S₂ State of Chlorocarbene," Journal of Chemical Physics, vol. 137, no. 10, American Institute of Physics (AIP), Sep 2012.
The definitive version is available at https://doi.org/10.1063/1.4748972
Keywords and Phrases
Bending excitation; CAS-SCF; Conical intersection; Corresponding state; Fluorescence lifetimes; Fundamental vibrations; High-level ab initio calculations; Isotopologues; Optical-optical double resonance; Pre-dissociation; Predissociation linewidths; Quasi-linear; Renner-Teller effect; Rotational constants; Rovibronic levels; Singlet manifold; Triplet state; Triplet surfaces; Vibrational levels; Fluorescence lifetimes; Fundamental vibrations; High-level ab initio calculations; Optical-optical double resonance; Predissociation linewidths; Renner-Teller effect; Rotational constants; Singlet and triplet state; Deuterium; Dynamics; Calculations; Dynamics; Excited states; Excited states; drug derivative; methane; article; chemistry; quantum theory; spectrophotometry; Methane; Quantum Theory; Spectrophotometry
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© 2012 American Institute of Physics (AIP), All rights reserved.
01 Sep 2012