Abstract
The calculations on the potential energy curves and spectroscopic constants of the ground and low-lying excited states of BrCl+, one of the important molecular ions in environment science, have been performed by using the multireference configuration interaction method at high level of theory in quantum chemistry. Through analyses of the effects of the spin-orbit coupling interaction on the electronic structures and spectroscopic properties, the multiconfiguration characteristic of the X2Π ground state and low-lying excited states was established. The spin-orbit coupling splitting energy of the X2Π ground state was calculated to be 1814 cm−1, close to the experimental value 2070 cm−1. The spin-orbit coupling splitting energy of the 2Π(II) exited state was predicted to be 766 cm−1. The transition dipole moments and Frank-Condon factors of the 3/2(III)-X3/2 and 1/2(III)-1/2(I) transitions were estimated, and the radiative lifetimes of the two transitions were briefly discussed.
Similar content being viewed by others
References
Barrie L A, Bottenheim J W, Schnell R C, Crutzen P J, Rasmussen R A. Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere. Nature, 1988, 334(6178): 138–141
Foster K L, Robert A P, Jan W B, Paul B S, Barbara J F, Chester W S. The role of Br2 and BrCl in surface ozone destruction at polar sunrise. Science, 2001, 291(5503): 471–474
Huber K P, Herzberg G. Molecular Spectra and Molecular Structure IV: Constants of Diatomic Molecules. New York: Van Nostrand Reinhold, 1979, 108
Beckert M, Wouters E R, Ashfold M N R, Wrede E. High resolution ion imaging study of BrCl photolysis in the wavelength range 330–570 nm. J Chem Phys, 2003, 119(18): 9576–9589
Straub P A, Mclean A D. Electronic structure of linear halogen compounds. Theor Chim Acta, 1974, 32(3): 227–242
Feller D, Peterson K A, de Jong W A, Dixon D A. Performance of coupled cluster theory in the thermochemical calculations of small halogenated compounds. J Chem Phys, 2003, 118(8): 3510–3522
Qiao Z M, Sun Q, Sun S T, Wang D X. Photoelectron spectroscopy and theoretical studies on bromine monochloride. Acta Chimica Sinica (in Chinese), 2004, 62(4): 433–435
Wang M, Wang B, Chen Z. Theoretical study on ground and low-lying excited electronic states of BrCl: Ab initio MRCI(SD)+Q calculations. J Mol Structure: Theochem, 2007, 806(1–3): 187–195
Dunlavey S J, Dyke J M, Morris A. Photoelectron spectrum of bromine monochloride. J Electron Spectrosc Relt Phenom, 1977, 12(3): 259–263
Nahler N H, Vieuxmaire O P J, Jones J R, Ashfold M N R, Eppink A T J B, Coriou A M, Parker D H. High-resolution ion-imaging studies of the photodissociation of the BrCl+ cation. J Phys Chem A, 2004, 108(39): 8077–8083
Vieuxmaire O P J, Nahler N H, Jones J R, Dixon R N, Ashfold M N R. Photodissociation of state selected BrCl+ cations: Branching ratios and angular anisotropies of the Br+ product forming channels. Mol Phys, 2005, 103(17): 2437–2452
Werner H J, Knowles P J, Amos R D, Bernhardsson A, Berning A, Celani P, Cooper D L, Deegan M J O, Dobbyn A J, Eckert F, Hampel C, Hetzer G, Korona T, Lindh R, Lloyd A W, McNicholas S J, Manby F R, Meyer W, Mura M E, Nicklass A, Palmieri P, Pitzer R, Rauhut G, Schutz M, Schumann U, Stoll H, Stone A J, Tarroni R, Thorsteinsson T. MOLPRO, a package of ab initio programs designed by Werner H J, Knowles P J. Version 2002. 6
Le Roy R J. LEVEL7.4: A Computer Program for Solving the Radial Schrödinger Equation for Bound and Quasibound Levels, University of Waterloo Chemical Physics Research Report CP-642R3, University of Waterloo, 2001
NIST Atomic Spectra Database, http://physics.nist.gov/cgi-bin/At-Data/main_asd.
Okabe H. Photochemistry of Small Molecules. New York: Wiley-Interscience, 1978. 231–232
Zou W, Liu W. Extensive theoretical studies on the low-lying electronic states of indium monochloride cation, InCl+. J Comput Chem 2005, 26(1): 106–113
Wang M, Wang B, Chen Z. Magnetic coupling interaction for mixed transition metal dimer: Ab initio MRCI(SD)+Q investigation on CrCu. Chem Phys Lett, 2007, 435: 5–9
Author information
Authors and Affiliations
Corresponding author
Additional information
Supported by the National Basic Research Program of China (Grant No. 2006CB601102) and the National Natural Science Foundations of China (Grant Nos. 20490210 and 20503001)
Rights and permissions
About this article
Cite this article
Wang, M., Wang, B. & Chen, Z. Theoretical study on potential energy curves and spectroscopy properties of ground and low-lying excited electronic states of BrCl+ . Sci. China Ser. B-Chem. 51, 521–528 (2008). https://doi.org/10.1007/s11426-007-0135-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-007-0135-4