Intensities of KCs $E(4)^1\Sigma^+\to (a^3\Sigma^+,X^1\Sigma^+)$ band system up to dissociation threshold: an interplay between spin-orbit, hyperfine and rovibronic coupling effects

TL;DR

This study analyzes the intensity distribution of the KCs molecule's band system up to dissociation, revealing how spin-orbit, hyperfine, and rovibronic couplings influence spectral intensities through a coupled-channels model.

Contribution

It introduces a coupled-channels deperturbation model using fixed electronic structure parameters to accurately describe spectral intensities up to the dissociation limit.

Findings

Strong competition between intramolecular interactions affects intensities.

Weak spin-orbit coupling causes $E\to a$ vibrational bands.

Hyperfine coupling influences intensity peculiarities near dissociation threshold.

Abstract

The relative intensity distribution in the rotationally resolved laser-induced fluorescence spectra belonging to the $E(4)^1\Sigma^+\to (a^3\Sigma^+_1,X^1\Sigma^+)$ band systems of the KCs molecule was analyzed. The experimental intensities in doublet $P$,$R$ progressions assigned to spin-allowed $E\to X$ and spin-forbidden $E\to a$ transitions up to their common ground dissociation limit were described in the framework of a coupled-channels (CC) deperturbation model applied for the interacting \Xstate\ and \astate\ states. The CC intensity simulation was based solely on fixed electronic structure parameters as functions of the internuclear distance $R$, namely: accurate empirical potential energy curves for all three states, \emph{ab initio} estimates for matrix elements $A(R)$ of the hyperfine structure (HFS) , and transition dipole moments $d_{EX}(R)$ and $d_{Ea}(R)$. A comparison between the measured intensities and their theoretical counterparts demonstrates a strong competition between different intramolecular interactions. A weak spin-orbit coupling of the upper \Estate\ state with the remote $^3\Pi$ states is responsible for appearance of the $E\to a$ vibrational bands for the intermediate $v_a$-values. In turn, the HFS coupling between \Xstate\ and \astate\ states leads to peculiarities in $E\to (X,a)$ intensities, which are pronounced for high $v_{X/a}$-values in the vicinity of K(4$^2S$)+Cs(6$^2S$) dissociation threshold. Both adiabatic ro-vibrational and non-adiabatic electronic-rotational interactions explain the abrupt deviation of some observed $P/R$ intensity ratios from the expected H\"{o}nl-London factors.