The Condon locus for a diatomic molecule is the locus, in the plane, of the strongest bands in an electronic band system. The form of the locus depends upon the form of the potential energy function of the electronic ...The Condon locus for a diatomic molecule is the locus, in the plane, of the strongest bands in an electronic band system. The form of the locus depends upon the form of the potential energy function of the electronic states involved. We show how the locus depends on the potential energy function for simple harmonic and anharmonic oscillators, first from a classical point of view, and then from a quantum mechanical point of view. One phenomenon of interest is that, in the case of anharmonic oscillators, the upper branch of the Condon locus traces much stronger bands than the lower branch. Another phenomenon, predicted by quantum mechanics but not by classical mechanics, is the existence of secondary nested Condon loci.展开更多
A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmon...A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmonic vibrational frequency calculations have been performed on the AX～U4（）1A1 state of O3 and AX～U4（）2B1 state of O-3. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of O-3. The theoretical spectrum obtained by employing CCSD（T）/6-311+G（2d,p） values are in excellent agreement with the observed one. In addition, the equilibrium geometry parameters, re（OO）= 0.135?5±0.000?5 nm and θe（O-O-O） =114.5±0.5°, of the AX～U4（）2B1 state of O-3, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.展开更多
文摘本文考虑多振动模混合和热带效应,凭借谐振子模型,推得计算两维-四振动模Franck-Condon重叠积分的解析表示,且应用于S_2O^-自由基光电子能谱的理论研究.对于S_2O(X^1A')—S_2O^-(X^2A")光脱附过程,结合分子轨道从头算和密度泛函理论,计算Franck-Condon因子,从而得到电子跃迁振动谱线的相对强度,理论上得到的光电子能谱与实验上观测到的能谱达到较好的一致;进一步在光谱模拟过程中,拟合实验能谱得到可靠的负离子自由基S_2O^-电子态(X^2A")的几何结构参数:键长R(SS)=2.008±0.005A和R(SO)=1.519±0.005 A.
文摘The Condon locus for a diatomic molecule is the locus, in the plane, of the strongest bands in an electronic band system. The form of the locus depends upon the form of the potential energy function of the electronic states involved. We show how the locus depends on the potential energy function for simple harmonic and anharmonic oscillators, first from a classical point of view, and then from a quantum mechanical point of view. One phenomenon of interest is that, in the case of anharmonic oscillators, the upper branch of the Condon locus traces much stronger bands than the lower branch. Another phenomenon, predicted by quantum mechanics but not by classical mechanics, is the existence of secondary nested Condon loci.
基金supports from the National Natural Science Foundation of China(No.21773221 and No.21827804)the National Key R&D Program of China(No.2017YFA0303502)the Fundamental Research Funds for the Central Universities of China(No.WK2340000078)。
基金SupportedbytheNationalNaturalScienceFoundationofChina(No.20073042)TheNaturalScienceFoundationofAnhuiProvince (No .2 0 0 1kj2 63zc)
文摘A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmonic vibrational frequency calculations have been performed on the AX～U4（）1A1 state of O3 and AX～U4（）2B1 state of O-3. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of O-3. The theoretical spectrum obtained by employing CCSD（T）/6-311+G（2d,p） values are in excellent agreement with the observed one. In addition, the equilibrium geometry parameters, re（OO）= 0.135?5±0.000?5 nm and θe（O-O-O） =114.5±0.5°, of the AX～U4（）2B1 state of O-3, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.
