Fourier-transform spectroscopy and deperturbation analysis of the spin-orbit coupled A(1)Sigma(+) and b(3)Pi states of KRb

摘要

Fourier-transform A(1)Sigma(+) - b(3)Pi -> X-1 Sigma(+) laser-induced fluorescence spectra were recorded for the natural mixture of (KRb)-K-39,41-Rb-85,87 isotopologues produced in a heatpipe oven. Overall 4200 rovibronic term values of the spin-orbit coupled A(1)Sigma(+) and b(3)Pi states were determined with an uncertainty of about 0.01 cm-1 in the energy range [10 850,14 200] cm(-1) covering rotational quantum numbers J' is an element of [3,280]. Direct deperturbation analysis of the A similar to b complex performed within the framework of the A(1)Sigma(+) similar to b(3)Pi(Omega=0,1,2) coupled-channel approach reproduced experimental data with a standard deviation of 0.004 cm(-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 similar to b complex for low J levels of (KRb)-K-39-Rb-85 as well as for (KRb)-K-41-Rb-87 isotopologues, allowing us to identify the most reasonable candidates for the stimulated Raman transitions between the initial uppermost vibrational levels of the a(3)Sigma(+) and X-1 Sigma(+) states, the intermediate levels of the A similar to b complex, and the lowest absolute ground X-1 Sigma(+)(v = 0, J = 0) state. Published by AIP Publishing.