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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 laserinduced fluorescence (LIF) $A\sim b\rightarrow X^1\Sigma^+_g$ Fourier transformspectra with the 0.01 cm$^{-1}$ uncertainty. The experimental term values ofthe $A^1\Sigma^+_u\sim b^3\Pi_u$ complex covering the rotational levels $J\in[4,395]$ in the excitation energy range $[9655,13630]$ cm$^{-1}$ were involvedinto coupled-channel (CC) deperturbation analysis. The deperturbation modeltakes 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 asspin-rotational interaction between the $\Omega=0$, $1$ and $2$ components ofthe $b^3\Pi^+_{\Omega_u}$ state. The \emph{ab initio} relativistic calculationson the low-lying electronic states of Cs$_2$ were accomplished in the frameworkof Fock space relativistic coupled cluster (FSRCC) approach to provide theinteratomic potentials of the interacting $A0^+_u$ and $b0^+_u$ states as wellas the relevant $A\sim b$ spin-orbit coupling function. To validate the presentCC deperturbation analysis solely obtained by energy-based data, the $A\sim b\to X(v^{\prime\prime}_X)$ LIF intensity distributions were measured andcompared with their theoretical counterparts obtained by means of thenon-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-fieldmethod.

physical review. a/physical review, a

Fourier transform spectroscopy, relativistic electronic structure  calculation, and coupled-channel deperturbation analysis of the fully mixed  $A^1\Sigma^+_u$ and $b^3\Pi_u$ states of Cs$_2$