Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations

Mok, Daniel K.W., Dyke, John and Lee, Edmond P.F. (2016) Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations. The Journal of Chemical Physics, 145 (24), 1-5. (doi:10.1063/1.4972816).

Record type: Article

Abstract

The photodetachment spectrum of HHfO? was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO?, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

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