Simulation of the single-vibronic-level emission spectra of HAsO and DAsO

• Published in: The Journal of chemical physics 2016-05, Vol.144 (18), p.184303-184303
• Main Authors: Mok, Daniel K. W., Lee, Edmond P. F., Dyke, John M.
• Format: Article
• Language: English
• Subjects: Anharmonicity; Computation; Computer simulation; Configuration interaction; Electron states; Electronic structure; Emission spectra; Mathematical analysis; Perturbation theory; Potential energy; Spectral emissivity
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4948648

The single-vibronic-level (SVL) emission spectra of HAsO and DAsO have been simulated by electronic structure/Franck-Condon factor calculations to confirm the spectral molecular carrier and to investigate the electronic states involved. Various multi-reference (MR) methods, namely, NEVPT2 (n-electron valence state second order perturbation theory), RSPT2-F12 (explicitly correlated Rayleigh-Schrodinger second order perturbation theory), and MRCI-F12 (explicitly correlated multi-reference configuration interaction) were employed to compute the geometries and relative electronic energies for the X ̃ 1 A ′ and A ̃ 1 A ″ states of HAsO. These are the highest level calculations on these states yet reported. The MRCI-F12 method gives computed T0 (adiabatic transition energy including zero-point energy correction) values, which agree well with the available experimental T0 value much better than previously computed values and values computed with other MR methods in this work. In addition, the potential energy surfaces of the X ̃ 1 A ′ and A ̃ 1 A ″ states of HAsO were computed using the MRCI-F12 method. Franck-Condon factors between the two states, which include anharmonicity and Duschinsky rotation, were then computed and used to simulate the recently reported SVL emission spectra of HAsO and DAsO [R. Grimminger and D. J. Clouthier, J. Chem. Phys. 135, 184308 (2011)]. Our simulated SVL emission spectra confirm the assignments of the molecular carrier, the electronic states involved, and the vibrational structures observed in the SVL emission spectra but suggest a loss of intensity in the reported experimental spectra at the low emission energy region almost certainly due to a loss of responsivity near the cutoff region (∼800 nm) of the detector used. Computed and experimentally derived r e (equilibrium) and/or r0 {the (0,0,0) vibrational level} geometries of the two states of HAsO are discussed.