论文标题
kcs $ e（4）^1σ^+\ to（a^3σ^+，x^1σ^+）$ band System to Oxociation阈值的强度：Spin-Orbit，Hyper-Fine和Rovibronic耦合效果之间的相互作用
Intensities of KCs $E(4)^1Σ^+\to (a^3Σ^+,X^1Σ^+)$ band system up to dissociation threshold: an interplay between spin-orbit, hyperfine and rovibronic coupling effects
论文作者
论文摘要
分析了属于$ e（4）^1σ^+\ to（a^3σ^+_ 1，x^1σ^+）$ band Systems的旋转激光诱导的荧光光谱。 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. CC强度模拟仅基于固定电子结构参数作为核对间距离$ r $的函数，即：对于所有三个状态的准确经验势能曲线，\ emph {ab initiO}矩阵元素$ a（r）$ a（r）超级精细结构（hfs）和过渡型d_ $ a（r） $ d_ {ea}（r）$。测得的强度及其理论对应物之间的比较表明，不同分子内相互作用之间存在浓厚的竞争。上层\ estate \ state与远程$^3π$状态的弱自旋轨道耦合负责$ e \ to $ e \ to $ e振动频段的中间$ v_a $ -values。反过来，\ xstate \和astate \ state之间的hfs耦合导致$ e \ to（x，a）$强度的特殊性，这些均为高$ v_ {x/a} $ - 在k（4 $^2s $）+cs（6 $^2s $）的近似值中发音。绝热的RO振动和非绝热电子旋转相互作用都解释了某些观察到的$ p/r $强度比与预期的Hönl-london因子的突然偏差。
The relative intensity distribution in the rotationally resolved laser-induced fluorescence spectra belonging to the $E(4)^1Σ^+\to (a^3Σ^+_1,X^1Σ^+)$ 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 $^3Π$ 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 Hönl-London factors.
