Simulation of the single-vibronic-level emission spectrum of HPS

Journal Article · Wed May 21 04:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4875806· OSTI ID:22254854

Mok, Daniel K. W.,; Chau, Foo-tim ^[1]; Lee, Edmond P. F., ^[1]; Dyke, John M. ^[2]

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1. Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom (Hong Kong)
2. School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom)

We have computed the potential energy surfaces of the X{sup ~1}A{sup ′} and A{sup ~1}A{sup ′′} states of HPS using the explicitly correlated multi-reference configuration interaction (MRCI-F12) method, and Franck–Condon factors between the two states, which include anharmonicity and Duschinsky rotation, with the aim of testing the assignment of the recently reported single-vibronic-level (SVL) emission spectrum of HPS [R. Grimminger, D. J. Clouthier, R. Tarroni, Z. Wang, and T. J. Sears, J. Chem. Phys. 139, 174306 (2013)]. These are the highest level calculations on these states yet reported. It is concluded that our spectral simulation supports the assignments of the molecular carrier, the electronic states involved and the vibrational structure of the experimental laser induced fluorescence, and SVL emission spectra proposed by Grimminger et al. [J. Chem. Phys. 139, 174306 (2013)]. However, there remain questions unanswered regarding the relative electronic energies of the two states and the geometry of the excited state of HPS.

• OSTI ID: 22254854
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CONFIGURATION INTERACTION
EMISSION SPECTRA
EXCITED STATES
FLUORESCENCE
POTENTIAL ENERGY
SIMULATION