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High-Level ab initio calculations on the X and A states of HGeCl and the equilibrium geometry of the A state derived from iterative franck-condon analysis of the SVL emission spectrum of HGeCl and DGeCl

High-Level ab initio calculations on the X and A states of HGeCl and the equilibrium geometry of the A state derived from iterative franck-condon analysis of the SVL emission spectrum of HGeCl and DGeCl
High-Level ab initio calculations on the X and A states of HGeCl and the equilibrium geometry of the A state derived from iterative franck-condon analysis of the SVL emission spectrum of HGeCl and DGeCl
CCSD(T) and/or CASSCF/MRCI calculations have been carried out on the 1A and Ã1A 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 1A state are re(HGe) = 1.580 ± 0.001 Å, e = 93.88 ± 0.01° and re(GeCl) = 2.170 ± 0.001 Å. 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 Ã1A 1A 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 Ã1A 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) structure for the 1A state, while varying the equilibrium geometrical parameters of the Ã1A state systematically.

Employing the derived IFCA geometry of re(HGe) = 1.590 Å, re(GeCl) = 2.155 Å and e(HGeCl) = 112.7° for the Ã1A 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.
ab inito calculations, spectral simulation with anharmonicity, absorption and emission spectra, HGeCl
1096-987X
476-491
Mok, Daniel K. W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Lee, Edmond P. F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Chau, Foo-Tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Mok, Daniel K. W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Lee, Edmond P. F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Chau, Foo-Tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f

Mok, Daniel K. W., Lee, Edmond P. F., Chau, Foo-Tim and Dyke, John M. (2010) High-Level ab initio calculations on the X and A states of HGeCl and the equilibrium geometry of the A state derived from iterative franck-condon analysis of the SVL emission spectrum of HGeCl and DGeCl. Journal of Computational Chemistry, 31 (3), 476-491. (doi:10.1002/jcc.21331).

Record type: Article

Abstract

CCSD(T) and/or CASSCF/MRCI calculations have been carried out on the 1A and Ã1A 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 1A state are re(HGe) = 1.580 ± 0.001 Å, e = 93.88 ± 0.01° and re(GeCl) = 2.170 ± 0.001 Å. 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 Ã1A 1A 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 Ã1A 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) structure for the 1A state, while varying the equilibrium geometrical parameters of the Ã1A state systematically.

Employing the derived IFCA geometry of re(HGe) = 1.590 Å, re(GeCl) = 2.155 Å and e(HGeCl) = 112.7° for the Ã1A 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.

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Published date: 2010
Keywords: ab inito calculations, spectral simulation with anharmonicity, absorption and emission spectra, HGeCl

Identifiers

Local EPrints ID: 147617
URI: http://eprints.soton.ac.uk/id/eprint/147617
ISSN: 1096-987X
PURE UUID: 05d50215-ccc1-4a1b-8f04-1ac4fcb39cf1
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 26 Apr 2010 08:29
Last modified: 07 Oct 2020 01:33

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