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中国物理学会期刊

基于ab initio计算的CF-离子低激发态光谱性质研究

CSTR: 32037.14.aps.66.023101

Spectroscopic properties of low-lying excited electronic states for CF- anion based on ab initio calculation

CSTR: 32037.14.aps.66.023101
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  • 基于相关一致基组aug-cc-pV5Z,采用高精度的内收缩多参考组态相互作用方法计算了CF-离子两个最低解离极限C(3P2)+F-(1S0)和C(1D2)+F-(1S0)对应的5个Λ-S态(X3Σ-,a1Δ,b1Σ+,A3Π和c31Π)的势能曲线.计算中考虑了Davidson修正和标量相对论修正以提高数据的可靠性.根据Λ-S态的势能曲线,求解径向薛定谔方程得到振转能级,通过拟合获得了这些电子态的光谱常数.此外,研究了5个Λ-S态的电偶极矩随核间距变化的曲线,分析了电子态的组态变化对电偶极矩的影响.计算了A3Π-X3Σ-的跃迁偶极矩和Franck-Condon因子,获得了A3Π的5个最低振动能级的辐射寿命,分析了两个电子态之间的跃迁特性,并给出了振子强度.最后,研究了A3Π态的预解离机理,并计算得到了高振动能级的解离寿命.

     

    CF- anion is very important for collisional ionization reactions, electron transfer from Rydberg atoms and electron attachment. Potential energy curves (PECs) of five low-lying excited electronic states, X3Σ-, a1Δ, b1Σ+, A3Π and c31Π of CF-, are calculated by using the internally contracted multireference configuration interaction (icMRCI) approach. Ro-vibrational levels of these electronic states are derived through solving the radial Schrödinger ro-vibrational equation, and then the molecular parameters are obtained by fitting. Our results for X3Σ- agree well with those in the references. We compute the electronic dipole moments (EDMs) of these states with different bound lengths, and analyze the relationship between the electronic configurations and EDMs. The electronic transition dipole moment matrix elements, Franck-Condon factors and oscillator strengths f00 of A3Π-X3Σ- are evaluated, and radiative lifetimes of five lowest vibrational levels of A3Π state are derived. Finally the predissociation mechanism of A3Π state is discussed in detail, and the dissociation lifetimes of high vibrational levels are obtained.

     

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