Ab Initio Calculations and Franck–Condon Simulation of the Absorption Spectra of GeCl<sub>2</sub> Including Anharmonicity

Mok, Daniel K. W.; Chau, Foo‐Tim; Lee, Edmond P. F.; Dyke, John M.

doi:10.1002/cphc.200400489

Cited by 9 publications

(1 citation statement)

References 33 publications

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“…The fitting of potential energy functions ͑PEFs͒ of the two electronic states involved, variational calculations of anharmonic vibrational wave functions, and FC factor calculations employing computed anharmonic vibrational wave functions and including allowance for Duschinsky rotation have been described previously, 27,28 and hence will not be repeated here. Nevertheless, some technical details specific to the present studies are summarized in Table II Table II͖ have been employed.…”

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confidence: 99%

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Lee

Mok

Chau

et al. 2010

The Journal of Chemical Physics

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Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} calculations were carried out on the X (2)B(1) and A (2)A(1) states of AsH(2) employing the fully relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to the augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d(10) electrons employing additional tight 4d3f2g2h functions designed for As. In addition, simplified, explicitly correlated CCSD(T)-F12 calculations were also performed employing different atomic orbital basis sets of up to aug-cc-pVQZ quality, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimate of the relative electronic energy of the A (2)A(1) state of AsH(2) relative to the X (2)B(1) state including zero-point energy correction (T(0)) is 19,954(32) cm(-1), which agrees very well with available experimental T(0) values of 19,909.4531(18) and 19,909.4910(17) cm(-1) obtained from recent laser induced fluorescence and cavity ringdown absorption spectroscopic studies. In addition, potential energy functions (PEFs) of the X (2)B(1) and A (2)A(1) states of AsH(2) were computed at different RCCSD(T) and CCSD(T)-F12 levels. These PEFs were used in variational calculations of anharmonic vibrational wave functions, which were then utilized to calculate Franck-Condon factors (FCFs) between these two states, using a method which includes allowance for anharmonicity and Duschinsky rotation. The A(0,0,0)-X single vibronic level (SVL) emission spectrum of AsH(2) was simulated using these computed FCFs. Comparison between simulated and available experimental vibrationally resolved spectra of the A(0,0,0)-X SVL emission of AsH(2), which consist essentially of the bending (2(n)) series, suggests that there is a significant loss in intensity in the low emission energy region of the experimental spectrum.

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Section: Labelmentioning

confidence: 99%

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Lee

Mok

Chau

et al. 2010

The Journal of Chemical Physics

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Vibrationally high-resolved electronic spectra of MCl 2 (M = C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl 2 −

Ran

Pang

Shen

et al. 2016

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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Franck–Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of AsF2− using ab initio calculations: Ionization energy and electron affinity of AsF2

Mok

Lee

Chau

et al. 2010

Phys. Chem. Chem. Phys.

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RCCSD(T) and/or CASSCF/MRCI calculations were carried out on the X(2)B(1) state of AsF(2), the X(1)A(1), ã(3)B(1) and A(1)B(1) states of AsF(2)(+), and the X(1)A(1) state of AsF(2)(-) employing the fully-relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d(10) electrons. In addition, simplified, explicitly correlated RHF/UCCSD(T)-F12x calculations were also performed employing different atomic orbital basis sets, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimates of the adiabatic ionization energies (AIE(0)) of AsF(2)(X(2)B(1)) to the X(1)A(1) and ã(3)B(1) states of AsF(2)(+), including corrections for zero-point vibrational energy (DeltaZPE), are 9.099(8) and 13.290(22) eV respectively. The best estimated electron affinity (EA(0)) of AsF(2) is 1.182(16) eV, also including Delta(ZPE). These are currently the most reliable AIE(0) and EA(0) values for AsF(2). Potential energy functions (PEFs) of the X(2)B(1) state of AsF(2), the X(1)A(1) and ã(3)B(1) states of AsF(2)(+) and X(1)A(1) state of AsF(2)(-) were computed at RCCSD(T)/aug-cc-pV5Z, RCCSD(T)/aug-cc-pCV5Z and RHF/UCCSD(T)-F12a/aug-cc-pCVTZ levels. These PEFs were employed in variational calculations of anharmonic vibrational wavefunctions, which were then utilised to calculate Franck-Condon factors (FCFs), using a method which includes allowance for anharmonicity and Duschinsky rotation. The computed FCFs were used to simulate the first two bands in the photoelectron spectrum of AsF(2) and the first band in the photodetachment spectrum of AsF(2)(-), both yet to be recorded. The simulated spectra obtained using different sets of PEFs were found to be almost identical, suggesting that the simplified explicitly correlated UCCSD(T)-F12x method with a relatively small basis set can be a reliable alternative to the conventional RCCSD(T) correlation methods with a relatively large basis set, but at a significantly lower cost.

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Ab Initio Calculations and Franck–Condon Simulation of the Absorption Spectra of GeCl₂ Including Anharmonicity

Cited by 9 publications

References 33 publications

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Vibrationally high-resolved electronic spectra of MCl 2 (M = C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl 2 −

Franck–Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of AsF2− using ab initio calculations: Ionization energy and electron affinity of AsF2

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Ab Initio Calculations and Franck–Condon Simulation of the Absorption Spectra of GeCl2 Including Anharmonicity

Cited by 9 publications

References 33 publications

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Ab initio calculations on the X̃ B21 and Ã A21 states of AsH2, and Franck–Condon simulation, including anharmonicity, of the Ã(,,)-X̃ single vibronic level emission spectrum of AsH2

Vibrationally high-resolved electronic spectra of MCl 2 (M = C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl 2 −

Franck–Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of AsF2− using ab initio calculations: Ionization energy and electron affinity of AsF2

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Ab Initio Calculations and Franck–Condon Simulation of the Absorption Spectra of GeCl₂ Including Anharmonicity