6533b856fe1ef96bd12b2f09

RESEARCH PRODUCT

Fourier-transform spectroscopy and relativistic electronic structure calculation on the c3Σ+ state of KCs

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Abstract The Ti:Saphire laser operated within 13800 - 11800 cm − 1 range was used to excite the c 3 Σ + state of KCs molecule directly from the ground X 1 Σ + state. The laser-induced fluorescence (LIF) spectra of the c 3 Σ + → a 3 Σ + transition were recorded with Fourier-transform spectrometer within 8000 to 10000 cm − 1 range. Overall 673 rovibronic term values belonging to both e / f -components of the c 3 Σ + ( Ω = 1 ± ) state of 39 KCs, covering vibrational levels from v = 0 to about 45, and rotational levels J ∈ [ 11 , 149 ] were determined with the accuracy of about 0.01 cm − 1 ; among them 7 values for 41 KCs. The experimental term values with v ∈ [ 0 , 22 ] were involved in a direct point-wise potential reconstruction for the c 3 Σ + ( Ω = 1 ± ) state, which takes into account the Ω -doubling effect caused by the spin-rotational interaction with the nearby c 3 Σ + ( Ω = 0 − ) state. The analysis and interpretation were facilitated by the fully-relativistic coupled cluster calculation of the potential energy curves for the B 1 Π , c 3 Σ + , and b 3 Π states, as well as of spin-forbidden c − X and spin-allowed c − a transition dipole moments; radiative lifetimes and vibronic branching ratios were calculated. A comparison of relative intensity distributions measured in vibrational c → a LIF progressions with their theoretical counterparts unambiguously confirms the vibrational assignment suggested in [J. Szczepkowski, et al., JQSRT, 204, 133–137 (2018)].