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首页> 外文期刊>The Journal of Chemical Physics >Dissociation of ground and n sigma* states of CF3CI using multireference configuration interaction with singles and doubles and with multireference average quadratic coupled cluster extensivity corrections
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Dissociation of ground and n sigma* states of CF3CI using multireference configuration interaction with singles and doubles and with multireference average quadratic coupled cluster extensivity corrections

机译：CF3CI的基态和n sigma *状态通过单，双精度多参考配置相互作用以及多参考平均二次耦合簇扩展性校正进行解离

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Extended complete active space self-consistent field (CASSCF),multireference configuration interaction with singles and doubles (MR-CISD),and multireference average quadratic coupled cluster (MR-AQCC) calculations have been performed on the ground (S0) and first excited (n sigma* ,S1) states of the CF3C1 molecule.Full geometry optimizations have been carried out for S0 as well as "relaxed" potential energy calculations for both states,along the C-Cl bond distance.Vertical excitation energies (DELTA E_(vertical)),dissociation energies (DELTA E_(diss)),dissociation enthalpies (DELTA H_(diss)),and the oscillator strength '(f) have also been computed.Basis set effects,basis set superposition error (BSSE),and spin-orbit and size-extensivity corrections have also been considered.The general agreement between theoretical and available experimental results is very good.The best results for the equilibrium geometrical parameters of S0 (at MR-AQCC/aug-cc-pVTZ+d level) are 1.762 and 1.323 A,for the C-Cl and C-F bond distances,respectively,while the corresponding experimental values are 1.751 and 1.328 A.The angle_(CLCF) and angle_(FCF) bond angles are in excellent agreement with the corresponding experimental values (110.3° and 108.6°).The best calculated values for DELTA E_(vertical),DELTA H_(diss) and f are 7.63 eV [at the MR-AQCC/aug-cc-pV(T+J)Z level],3.59 eV [MR-AQCC/aug-cc-pV(T+d)Z level+spin-orbit and BSSE corrections],and 2.74X10~(-3) (MR-CISD/cc-pVTZ),in comparison with the corresponding experimental values of 7.7±0.1 eV,3.68 eV,and 3.12 X 10_3±2.50 X 10~4.The results concerning the potential energy curves for S0 and Si show a tendency toward the nonoccurrence of crossing between these two states (in the intermediate region along the C-Cl coordinate),as the basis set size increases.Such tendency is accompanied by a decreasing well depth for the S1 state.Dynamic electronic correlation (especially at the MR-AQCC level) is also an important factor toward an absence of crossing along the C-Cl coordinate.Further investigations of a possible crossing using gradient driven techniques (at CASSCF and MR-CISD levels) seem to confirm its absence.
机译：扩展的完整活动空间自洽场（CASSCF），与单双打的多参考配置交互（MR-CISD）和多参考平均二次耦合簇（MR-AQCC）计算已在地面（S0）上进行了首次激发（ CF3C1分子的n sigma *，S1）状态。已针对S0进行了完整的几何优化，并针对两种状态沿C-Cl键距进行了“松弛”势能计算。垂直激发能（DELTA E_（vertical ）），离解能（DELTA E_（diss）），离解焓（DELTA H_（diss））和振子强度'（f）也已计算出来。基础设定效应，基础设定叠加误差（BSSE）和自旋还考虑了轨道和尺寸扩展校正。理论和可用的实验结果之间的总体一致性很好.S0的平衡几何参数的最佳结果（在MR-AQCC / aug-cc-pVTZ + d水平）分别为1.762和1.323 A C-Cl和CF键的距离分别为1.751和1.328 A.angle_（CLCF）和angle_（FCF）键角与相应的实验值（110.3°和108.6°）高度吻合。对于DELTA E_（垂直），DELTA H_（diss）和f的最佳计算值是7.63 eV [在MR-AQCC / aug-cc-pV（T + J）Z级别]，3.59 eV [MR-AQCC / aug-cc-pV（T + d）Z水平+自旋轨道和BSSE校正]和2.74X10〜（-3）（MR-CISD / cc-pVTZ），与相应的实验值7.7±0.1进行比较eV，3.68 eV和3.12 X 10_3±2.50 X 10〜4。有关S0和Si的势能曲线的结果表明，这两种状态之间不发生交叉趋势（在沿C-Cl坐标的中间区域） ），随着基础集大小的增加。这种趋势伴随着S1状态的阱深度减小。动态电子相关性（尤其是在MR-AQCC级别）也是导致不存在cr的重要因素沿C-Cl坐标摆动。使用梯度驱动技术（在CASSCF和MR-CISD水平）对可能穿越的进一步研究似乎证实了其不存在。

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