An experimental and theoretical study of the electronic spectrum of the HBCl free radical

Journal Article · Wed Jan 07 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4904892· OSTI ID:22415457

Gharaibeh, Mohammed A. ^[1]; Nagarajan, Ramya; Tarroni, Riccardo ^[2]

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1. Department of Chemistry, The University of Jordan, Amman 11942 (Jordan)
2. Dipartimento di Chimica Industriale “Toso Montanari,” Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy)

Following our previous discovery of the spectra of the HBX (X = F, Cl, and Br) free radicals [S.-G. He, F. X. Sunahori, and D. J. Clouthier, J. Am. Chem. Soc. 127, 10814 (2005)], the A{sup ~2}A{sup ″}Π−X{sup ~2}A{sup ′} band systems of the HBCl and DBCl free radicals have been studied in detail. The radicals have been prepared in a pulsed electric discharge jet using a precursor mixture of BCl{sub 3} and H{sub 2} or D{sub 2} in high pressure argon. Laser-induced fluorescence (LIF) and single vibronic level emission spectra have been recorded to map out the ground and excited state vibrational energy levels. The band system involves a linear-bent transition between the two Renner-Teller components of what would be a {sup 2}Π electronic state at linearity. We have used high level ab initio theory to calculate the ground and excited state potential energy surfaces and have determined the vibronic energy levels variationally. The theory results were used to assign the LIF spectra which involve transitions from the ground state zero-point level to high vibrational levels of the excited state. The correspondence between theory and experiment, including the transition frequencies, upper state band symmetries, and H, B, and Cl isotope shifts, was used to validate the assignments.

• OSTI ID: 22415457
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ARGON
BORON CHLORIDES
CHLORINE ISOTOPES
DEUTERIUM
ELECTRIC DISCHARGES
EMISSION SPECTRA
EXCITED STATES
FLUORESCENCE
GROUND STATES
HYDROGEN
LASER RADIATION
LITHIUM FLUORIDES
MIXTURES
POTENTIAL ENERGY
SYMMETRY
VARIATIONAL METHODS