Symmetry breaking in the NO2 σ radical: Construction of the 2A1 and 2B2 states with Cs symmetry complete active space self‐consistent‐field wave functions
Symmetry breaking in the NO2 σ radical: Construction of the 2A1 and 2B2 states with Cs symmetry complete active space self‐consistent‐field wave functions
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NO2 σ自由基中的对称性破缺：构建具有Cs对称性的2A1和2B2态完整活性空间自洽场波函数
DOI：
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发表时间：
1990
期刊：
影响因子：
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通讯作者：
H. Schaefer
中科院分区：
文献类型：
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作者：
Charles P. Blahous;B. Yates;Yaoming Xie;H. Schaefer
Jackels和Davidson对NO2自由基中对称破缺问题的解释使用完全活性空间自洽场（CASSCF）波函数进行了检验。Jackels和Davidson对2B 2 NO2的C2 v-限制波函数的必要形式进行了刘易斯-结构分析。特别是，C2 v和单组态限制迫使分子在共振的有利影响和波函数中包含带电成分的不利影响之间进行“选择”。根据Jackels和Davidson的说法，这种选择会导致2B 2最小值区域的Cs对称性失真。Cs对称性完整的活性空间处理使NO2能够实现适当对称性的波函数（对于2A 1和2B 2状态，当C2 v核对称性存在时），同时产生显着的局部轨道，从而提供了一种方法来验证早期的分析。虽然Cs完全活性空间的结果矛盾的一个重要Jackels-Davidson r...
Jackels and Davidson’s interpretation of the symmetry‐breaking problem in the NO2 radical is examined using complete active space self‐consistent‐field (CASSCF) wave functions. Jackels and Davidson provided a Lewis‐structure analysis of the necessary forms of C2v ‐restricted wave functions for 2B2 NO2. In particular, C2v and single‐configuration restrictions force the molecule to ‘‘choose’’ between the beneficial effects of resonance and the adverse effects of inclusion of charged components in the wave function. This choice, according to Jackels and Davidson, results in a distortion to Cs symmetry in the region of the 2B2 minimum. The Cs symmetry complete active space treatment enables NO2 to achieve wave functions of proper symmetry (for both 2A1 and 2B2 states, when C2v nuclear symmetry is present) while simultaneously yielding significantly localized orbitals, thus offering a means to verify the earlier analysis. Although the Cs complete active space results contradict one important Jackels–Davidson r...