Fourier-transform spectroscopy and deperturbation analysis of the spin-orbit coupled A{sup 1}Σ{sup +} and b{sup 3}Π states of KRb
Fourier-transform A{sup 1}Σ{sup +} − b{sup 3}Π → X{sup 1}Σ{sup +} laser-induced fluorescence spectra were recorded for the natural mixture of {sup 39,41}K{sup 85,87}Rb isotopologues produced in a heatpipe oven. Overall 4200 rovibronic term values of the spin-orbit coupled A{sup 1}Σ{sup +} and b{sup 3}Π states were determined with an uncertainty of about 0.01 cm{sup −1} in the energy range [10 850, 14 200] cm{sup −1} covering rotational quantum numbers J′ ∈ [3, 280]. Direct deperturbation analysis of the A ∼ b complex performed within the framework of the A{sup 1}Σ{sup +} ∼ b{sup 3}Π{sub Ω=0,1,2} coupled-channel approach reproduced experimental data with a standard deviation of 0.004 cm{sup −1}. Initial parameters of the internuclear potentials and spin-orbit coupling functions along with the relevant transition dipole moments were obtained by performing the quasi-relativistic electronic structure calculations. The mass-invariant molecular parameters obtained from the fit were used to predict energy and radiative properties of the A ∼ b complex for low J levels of {sup 39}K{sup 85}Rb as well as for {sup 41}K{sup 87}Rb isotopologues, allowing us to identify the most reasonable candidates for the stimulated Raman transitions between the initial uppermost vibrational levels of the a{sup 3}Σ{sup +} and X{sup 1}Σ{sup +} states, the intermediate levels of the A ∼ b complex, and the lowest absolute ground X{sup 1}Σ{sup +}(v = 0, J = 0) state.
- OSTI ID:
- 22657912
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 14; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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