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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >X,A,B,C,and D States of the C_6H_5F~+ Ion Studied Using Multiconfiguration Wave Functions
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X,A,B,C,and D States of the C_6H_5F~+ Ion Studied Using Multiconfiguration Wave Functions

机译：使用多配置波函数研究C_6H_5F〜+离子的X，A，B，C和D状态

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摘要

Electronic states of the C_6H_5F~+ ion have been studied within C_(2v)symmetry by using the complete active space self-consistent field(CASSCF)and multiconfiguration second-order perturbation theory(CASPT2)methods in conjunction with an atomic natural orbital basis.Vertical excitation energies(T_v)and relative energies(TV)at the ground-state geometry of the C_6H_5F molecule were calculated for 12 states.For the five lowest-lying states,1~2B_1,1~2A_2,2~2B_1,1~2B_2,and 1~2A_1,geometries and vibrational frequencies were calculated at the CASSCF level,and adiabatic excitation energies(7b)and potential energy curves(PEC)for F-loss dissociations were calculated at the CASPT2//CASSCF level.On the basis of the CASPT2 T_0 calculations,we assign the X,A,B,C,and D states of the ion to 1~2B_1,1~2A_2,2~2B_1,1~2B_2,and 1~2A_1,respectively,which supports the suggested assignment of the B state to(2)_2B_1 by Anand et al.based on their experiments.Our CASPT2 TV and TV calculations and our MRCI T_0,T_v,and TV calculations all indicate that the 2~2B_1 state of C_6H_5F~+ lies below 1~2B_2.By checking the relative energies of the asymptote products and checking the fragmental geometries and the charge and spin density populations in the asymptote products along the CASPT2//CASSCF PECs,we conclude that the 1~2B_1,1~2B_2,and 1~2A_1 states of C_6H_5F~+ correlate with C_6H_5+(1~1A_1)+ F(~2P)(the first dissociation limit).The energy increases monotonically along the 1~2B_1 PEC,and there are barriers and minima along the 1~2B_2 and 1~1A_1 PECs.The predicted appearance potential value for C_6H_5~+(1~1A_1)is very close to the average of the experimental values.Our CASPT2//CASSCF PEC calculations have led to the conclusion that the 1~2A_2 state of C_6H_5F~+ correlates with the third dissociation limit of C_6H_5~+(1~1A_2)+ F(~2P),and a preliminary discussion is presented.
机译：利用完整的有源空间自洽场（CASSCF）和多构型二阶摄动理论（CASPT2）方法，结合原子自然轨道，研究了C_（2v）对称性下的C_6H_5F〜+离子的电子态。计算了12种状态下C_6H_5F分子基态几何结构的垂直激发能（T_v）和相对能（TV）。对于五个最低处的状态，1〜2B_1,1〜2A_2,2〜2B_1,1〜在CASSCF级计算2B_2和1〜2A_1的几何形状和振动频率，并在CASPT2 // CASSCF级计算F损耗解离的绝热激发能（7b）和势能曲线（PEC）。在CASPT2 T_0计算中，我们分别将离子的X，A，B，C和D状态分配给1〜2B_1、1〜2A_2、2〜2B_1、1〜2B_2和1〜2A_1，它们支持建议根据Anand等人的实验将B状态分配给（2）_2B_1。我们的CASPT2 TV和TV计算以及我们的MRCI T_0，T_v电视计算均表明C_6H_5F〜+的2〜2B_1状态在1〜2B_2以下。通过检查渐近线产物的相对能量，并检查沿着CASPT2 /的渐近线产物的碎片几何以及电荷和自旋密度种群。 / CASSCF PECs，我们得出结论C_6H_5F〜+的1〜2B_1、1〜2B_2和1〜2A_1状态与C_6H_5 +（1〜1A_1）+ F（〜2P）（第一解离极限）相关。能量单调增加沿1〜2B_1 PEC沿途，并且沿1〜2B_2和1〜1A_1 PEC沿途有障碍和极小值.C_6H_5〜+（1〜1A_1）的预测出现电势值非常接近实验值的平均值。 CASPT2 // CASSCF PEC计算得出的结论是C_6H_5F〜+的1〜2A_2状态与C_6H_5〜+（1〜1A_2）+ F（〜2P）的第三解离限相关，并进行了初步讨论。

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