We have studied the tetra-atomic Renner–Teller effect in the ground state of the jet-cooled HCCS and DCCS free radicals. The reactive intermediates were produced in a pulsed discharge jet using thiophene or deuterated thiophene precursors and the ground-state vibronic energies were measured using the single vibronic level emission spectroscopy technique. In HCCS, emission and fluorescence depletion experiments proved that some previously unassigned laser-induced fluorescence (LIF) features were anomalous transitions, which gave information on several ground-state levels. In DCCS, rotational mixing of the excited state level with the level allowed several ground-state levels to be observed in emission. In addition, we have shown that some previously unassigned weak LIF bands of DCCS are anomalous transitions which have allowed us to accurately measure the ground-state spin-orbit splitting for the first time. All of the expected ground-state levels and the majority of the levels up to have been observed for both isotopomers. The data have been fitted by an effective Hamiltonian matrix treatment that included Renner–Teller, spin-orbit coupling, anharmonicity, and Fermi resonance effects for the two bending vibrations and the CS stretching mode. This has allowed an unusually complete description of the orbital angular momentum coupling effects, including the determination of the , , and terms for the first time. Subtle effects in both the LIF and emission spectra signal the presence of Sears resonances in both the ground and excited states of these radicals.
Skip Nav Destination
Article navigation
1 July 2005
Research Article|
July 14 2005
Renner–Teller vibronic analysis for a tetra-atomic molecule. II. The ground state of the HCCS free radical
Sheng-Gui He;
Sheng-Gui He
Department of Chemistry,
University of Kentucky
, Lexington, Kentucky 40506-0055
Search for other works by this author on:
Dennis J. Clouthier
Dennis J. Clouthier
a)
Department of Chemistry,
University of Kentucky
, Lexington, Kentucky 40506-0055
Search for other works by this author on:
a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 123, 014317 (2005)
Article history
Received:
April 05 2005
Accepted:
April 29 2005
Connected Content
A companion article has been published:
Renner–Teller vibronic analysis for a tetra-atomic molecule. I. The effective Hamiltonian and matrix elements
Citation
Sheng-Gui He, Dennis J. Clouthier; Renner–Teller vibronic analysis for a tetra-atomic molecule. II. The ground state of the HCCS free radical. J. Chem. Phys. 1 July 2005; 123 (1): 014317. https://doi.org/10.1063/1.1938948
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
The laser-induced fluorescence spectrum, Renner–Teller effect, and molecular quantum beats in the à 2 Π i -X̃ 2 Π i transition of the jet-cooled HCCSe free radical
J. Chem. Phys. (September 2004)
The molecular structure and a Renner-Teller analysis of the ground and first excited electronic states of the jet-cooled C S 2 + molecular ion
J. Chem. Phys. (February 2006)
Renner–Teller effect in linear tetra-atomic molecules. II. Rovibronic levels analysis of the X Π 2 u electronic state of HCCH +
J. Chem. Phys. (April 2009)