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Title: High-level Ab initio calculations on HGeCl and the equilibrium geometry of the (A)over-tilde(1)A '' state derived from Franck-Condon analysis of the single-vibronic-level emission spectra of HGeCl and DGeCl
Authors: Mok, DKW 
Chau, FT
Lee, EPF
Dyke, JM
Keywords: Ab inito calculations
Spectral simulation with anharmonicity
Absorption and emission spectra
Issue Date: 2010
Publisher: Wiley-Blackwell
Source: Journal of computational chemistry, 2010, v. 31, no. 3, p. 476-491 How to cite?
Journal: Journal of Computational Chemistry 
Abstract: CCSD(T) and/or CASSCF/MRCI calculations have been carried out oil the (X) over tilde (1)A', and (A) over tilde (1)A '' states of HGeCl. The fully relativistic effective core potential, ECP10MDF, and associated standard valence basis sets of up to the aug-cc-pV5Z quality were employed for Ge. Contributions from core correlation and extrapolation to the complete basis set limit were included in determining the computed equilibrium geometrical parameters and relative electronic energy of these two states of HGeCl. Based on the currently, most systematic CCSD(T) calculations performed in this study, the best theoretical geometrical parameters of the (X) over tilde (1)A' state are r(e)(HGe) = 1.580 +/- 0.001 angstrom, theta(e) = 93.88 +/- 0.01 degrees and r(e)(GeCl) = 2.170 +/- 0.001 angstrom. In addition, Franck-Condon factors including allowance for anharmonicity and Duschinsky rotation between these two states of HGeCl and DGeCl were calculated employing CCSD(T) and CASSCF/MRCI potential energy functions, and were used to simulate (A) over tilde (1)A '' -> (X) over tilde (1)A' SVL emission spectra of HGeCl and DGeCl. The iterative Franck-Condon analysis (IFCA) procedure was carried out to determine the equilibrium geometrical parameters of the (A) over tilde (1)A '' state of HGeCl by matching the simulated, and available experimental SVL emission spectra of HGeCl and DGeCl of Tackett et al., J Chem Phys 2006, 124, 124320, using the available, estimated experimental equilibrium (r(e)(z)) structure for the (X) over tilde (1)A' state, while varying the equilibrium geometerical parameters of the (A) over tilde (1)A '' state systematically. Employing the derived IFCA geometry of r(e)(HGe) = 1.590 angstrom, r(e)(GeCl) = 2.155 angstrom and theta(e)(HGeCl) = 112.7 degrees for the (A) over tilde (1)A '' state of HGeCl in the spectral simulation, the simulated absorption and SVL emission spectra of HGeCl and DGeCl agree very well with the available experimental LIF and SVL emission spectra, respectively.
ISSN: 0192-8651
DOI: 10.1002/jcc.21331
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