X (1)A(') SVL emission of HSiF. Discrepancies between the simulated and observed spectra of the A (1)A(")(0,1,0) and (1,1,0) SVL emissions of HSiF have been found. These are most likely, partly due to experimental deficiencies and, partly to inadequacies in the ab initio levels of theory employed in the calculation of the PEFs. Based on the computed Franck-Condon factors, minor revisions of previous vibrational assignments are suggested. The calculated anharmonic wave functions of higher vibrational levels of the X (1)A(') state show strong mixings between the three vibrational modes of HSi stretching, bending, and SiF stretching." />
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Mok DK, Lee EP, Chau FT, et al. Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity. J Chem Phys. 2004;120(3):1292-305doi: 10.1063/1.1630559.
Mok, D. K., Lee, E. P., Chau, F. T., & Dyke, J. M. (2004). Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity. The Journal of chemical physics, 120(3), 1292-305. https://doi.org/10.1063/1.1630559
Mok, Daniel K W, et al. "Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity." The Journal of chemical physics vol. 120,3 (2004): 1292-305. doi: https://doi.org/10.1063/1.1630559
Mok DK, Lee EP, Chau FT, Dyke JM. Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity. J Chem Phys. 2004 Jan 15;120(3):1292-305. doi: 10.1063/1.1630559. PMID: 15268255.
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J Chem Phys. 2004 Jan 15;120(3):1292-305. doi: 10.1063/1.1630559.

Franck-Condon simulation of the single vibronic level emission spectra of HSiF and DSiF including anharmonicity.

The Journal of chemical physics

Daniel K W Mok, Edmond P F Lee, Foo-Tim Chau, John M Dyke

Affiliations

  1. Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong. [email protected]

PMID: 15268255 DOI: 10.1063/1.1630559

Abstract

Potential energy functions (PEFs) of the X (1)A(') and A (1)A(") states of HSiF have been computed using the coupled-cluster single-double plus perturbative triple excitations and complete-active-space self-consistent-field multireference internally contracted configuration interaction methods, respectively, employing augmented correlation-consistent polarized-valence quadruple-zeta basis sets. For both electronic states of HSiF and DSiF, anharmonic vibrational wavefunctions and energies of all three modes have been calculated variationally with the ab initio PEFs and using Watson's Hamiltonian for nonlinear molecules. Franck-Condon factors between the two electronic states, allowing for Duschinsky rotation, were computed using the calculated anharmonic vibrational wavefunctions. These Franck-Condon factors were used to simulate the single vibronic level (SVL) emission spectra recently reported by Hostutler et al. in J. Chem. Phys. 114, 10728 (2001). Excellent agreement between the simulated and observed spectra was obtained for the A (1)A(")(1,0,0)-->X (1)A(') SVL emission of HSiF. Discrepancies between the simulated and observed spectra of the A (1)A(")(0,1,0) and (1,1,0) SVL emissions of HSiF have been found. These are most likely, partly due to experimental deficiencies and, partly to inadequacies in the ab initio levels of theory employed in the calculation of the PEFs. Based on the computed Franck-Condon factors, minor revisions of previous vibrational assignments are suggested. The calculated anharmonic wave functions of higher vibrational levels of the X (1)A(') state show strong mixings between the three vibrational modes of HSi stretching, bending, and SiF stretching.

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