Experimental and Theoretical Studies of the Electronic Transitions of BeC
Abstract
Electronic spectra for BeC have been recorded over the range 30 500-40 000 cm-1. Laser ablation and jet-cooling techniques were used to obtain rotationally resolved data. The vibronic structure consists of a series of bands with erratic energy spacings. Two-color photoionization threshold measurements were used to show that the majority of these features originated from the ground state zero-point level. The rotational structures were consistent with the bands of 3Π-X3Σ- transitions. Theoretical calculations indicate that the erratic vibronic structure results from strong interactions between the four lowest energy 3Π states. Adiabatic potential energy curves were obtained from dynamically weighted MRCI calculations. Diabatic potentials and coupling matrix elements were then reconstructed from these results, and used to compute the vibronic energy levels for the four interacting 3Π states. The predictions were sufficiently close to the observed structure to permit partial assignment of the spectra. Bands originating from the low-lying 15Σ- state were also identified, yielding a 5Σ- to X 3Σ- energy interval of 2302 ± 80 cm -1 and molecular constants for the 15Π state. The ionization energy of BeC was found to be 70 779(40) cm-1.
Recommended Citation
B. J. Barker et al., "Experimental and Theoretical Studies of the Electronic Transitions of BeC," Journal of Chemical Physics, vol. 137, no. 21, American Institute of Physics (AIP), Dec 2012.
The definitive version is available at https://doi.org/10.1063/1.4768548
Department(s)
Chemistry
Keywords and Phrases
Adiabatic potential energy curves; Coupling matrix element; Diabatic potentials; Electronic spectrum; Electronic transition; Energy interval; Energy spacings; Molecular constants; Photoionization threshold; Rotational structures; Strong interaction; Theoretical calculations; Theoretical study; Two-color; Vibronic energy levels; Vibronic structure; Zero-point, Physics, Physical chemistry
International Standard Serial Number (ISSN)
0021-9606
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2012 American Institute of Physics (AIP), All rights reserved.
Publication Date
01 Dec 2012
