Fourier-transform spectroscopy, relativistic electronic structure calculation, and coupled-channel deperturbation analysis of the fully mixed A1Σu+ and b3Πu states of Cs2

Abstract

The 4503 rovibronic term values belonging to the mutually perturbed $A^1\Sigma^+_u$ and $b^3\Pi_u$ states of Cs$_2$ were extracted from laser induced fluorescence (LIF) $A\sim b\rightarrow X^1\Sigma^+_g$ Fourier transform spectra with the 0.01 cm$^{-1}$ uncertainty. The experimental term values of the $A^1\Sigma^+_u\sim b^3\Pi_u$ complex covering the rotational levels $J\in [4,395]$ in the excitation energy range $[9655,13630]$ cm$^{-1}$ were involved into coupled-channel (CC) deperturbation analysis. The deperturbation model takes explicitly into account spin-orbit coupling of the $A^1\Sigma^+_u(A0^+_u)$ and $b^3\Pi^+_{0_u}(b0^+_u)$ states as well as spin-rotational interaction between the $\Omega=0$, $1$ and $2$ components of the $b^3\Pi^+_{\Omega_u}$ state. The \emph{ab initio} relativistic calculations on the low-lying electronic states of Cs$_2$ were accomplished in the framework of Fock space relativistic coupled cluster (FSRCC) approach to provide the interatomic potentials of the interacting $A0^+_u$ and $b0^+_u$ states as well as the relevant $A\sim b$ spin-orbit coupling function. To validate the present CC deperturbation analysis solely obtained by energy-based data, the $A\sim b \to X(v^{\prime\prime}_X)$ LIF intensity distributions were measured and compared with their theoretical counterparts obtained by means of the non-adiabatic vibrational wave functions of the $A\sim b$ complex and the FSRCC $A\sim b \to X$ transition dipole moments calculated by the finite-field method.