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We combined high-resolution Fourier-transform spectroscopy and large-scaleelectronic structure calculation to study energy and radiative properties ofthe high-lying (3)1{\Pi} and (5)1{\Sigma}+ states of the RbCs molecule. Thelaser-induced (5)1{\Sigma}+(4)1{\Sigma}+(3)1{\Pi}-A(2)1{\Sigma}+ b(1)3{\Pi}fluorescence (LIF) spectra were recorded by the Bruker IFS-125(HR) spectrometerin the frequency range {\nu} 5500 to 10000cm-1 with the instrumental resolutionof 0.03 cm-1. The rotational assignment of the observed LIF progressions, whichexhibit irregular vibrational-rotational spacing due to strong spin-orbitinteraction between A1{\Sigma}+ and b3(\Pi) states was based on thecoincidences between observed and calculated energy differences. The requiredrovibronic term values of the strongly perturbed A-b complex have beencalculated by a coupled-channels approach for both 85Rb133Cs and 87Rb133Csisotopologs with accuracy of about 0.01 cm-1, as demonstrated in A. Kruzins etal. [J. Chem. Phys. 141, 184309 (2014)]. The experimental energies of the upper(3)1(\Pi) and (5)1{\Sigma}+ states were involved in a direct-potential-fitanalysis performed in the framework of inverted perturbation approach.Quasirelativistic ab initio calculations of the spin-allowed(3)1{\Pi},(5)1{\Sigma}+- (1-4)1{\Sigma}+(1-3)1{\Pi} transition dipole momentswere performed. Radiative lifetimes and vibronic branching ratios of radiativetransitions from the (3)1{\Pi} and (5)1{\Sigma}+ states were evaluated. Toelucidate the origin of the {\Lambda}-doubling effect in the (3)1{\Pi} state,the angular coupling (3)1{\Pi}-(1-5)1{\Sigma}+ electronic matrix elements werecalculated and applied for the relevant q-factors estimate. The intensitydistributions simulated for the particular (5)1{\Sigma}+(3)1{\Pi}-A-b LIFprogressions have been found to be remarkably close to their experimentalcounterparts.

Energy and radiative properties of the (3)1{\Pi} and (5)1{\Sigma}+ states of RbCs: Experiment and theory