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凭借密度泛函理论,采用不同基组对中性分子CrO2的基态(X3 B1)以及阴离子CrO2-的基态(X4B1)进行几何优化和振动频率分析;应用量化计算得到的力常数及结构和光谱参数,基于推得的两维四模Franck-Condon重叠积分的代数表示,对CrO2(X3 B1)-CrO2-(X4 B1)的光脱附过程进行Franck-Condon分析和光谱模拟,理论上得到光电子能谱的谱线相对强度及振动结构分布,理论谱与实验测得的二氧化铬阴离子光电子能谱达到一致,并对光电子能谱的振动结构进行归属及热带分析;另外,在光谱模拟过程中通过迭代Franck-Condon分析过程,推得CrO2-(X4 B1)与CrO2(X3 B1)平衡几何结构之差:ΔR(Cr-O)=0.05,Δ∠(O-Cr-O)=12°.
Based on the density functional theory (DFT), the geometrical optimization and vibrational frequency analysis of the ground state (X3 B1) of the neutral molecular CrO2 and the ground state of the anion CrO2- (X4B1) were performed using different basis sets. The force constants and structural and spectral parameters , The Franck-Condon analysis and spectral simulation of the photodetachment process of CrO2 (X3 B1) -CrO2- (X4 B1) were carried out based on the algebraic representation of the deduced two-dimensional four-mode Franck-Condon overlap integral. The relative intensities of the spectral lines and the distribution of the vibrational structures are also consistent. The theoretical spectra are consistent with the experimental chromoanion photoelectron spectra, and the vibrational structures of the photoelectron spectra are assigned and analyzed by tropical analysis. In addition, Iteration of the Franck-Condon analysis shows that the difference in equilibrium geometry between CrO2- (X4 B1) and CrO2 (X3 B1) is ΔR (Cr-O) = 0.05 and Δ∠ (O-Cr-O) = 12 °.