Applied quantum chemistry: Spectroscopic detection and characterization of the F{sub 2}BS and Cl{sub 2}BS free radicals in the gas phase

Journal Article · Sat Mar 28 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4915126· OSTI ID:22415558

Jin, Bing; Sheridan, Phillip M. ^[1]

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1. Department of Chemistry and Biochemistry, Canisius College, Buffalo, New York 14208 (United States)

In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X{sub 2}BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F{sub 2}BS and Cl{sub 2}BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF{sub 3} or BCl{sub 3} and CS{sub 2} vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B{sup ~2}A{sub 1}–X{sup ~} {sup 2}B{sub 2} laser-induced fluorescence spectra were found within 150 cm{sup −1} of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B{sup ~2}A{sub 1} state emits down to the ground state and to the low-lying A{sup ~2}B{sub 1} excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B{sup ~}–X{sup ~} band system of Cl{sub 2}BS is evident, as signaled by the activity in the b{sub 2} modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B{sup ~2}A{sub 1} state with a nearby electronic state of {sup 2}B{sub 2} symmetry.

• OSTI ID: 22415558
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
BORON CHLORIDES
BORON FLUORIDES
CARBON SULFIDES
CHEMISTRY
COMPUTERIZED SIMULATION
COUPLING
ELECTRIC DISCHARGES
EMISSION SPECTRA
EXCITED STATES
FLUORESCENCE SPECTROSCOPY
FRANCK-CONDON PRINCIPLE
GROUND STATES
HALOGENS
MOLECULAR BEAMS
PRECURSOR
RADICALS