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采用运动方程单双取代耦合团簇理论(EOM-CCSD)对XF3(X=N,P,As)的价层垂直离势(VIP)进行了系统计算,同时对称匹配团簇组态相互作用(SAC-CI)、外价层格林函数(OVGF)以及部分三阶近似(P3)方法也被应用到目前计算.与已有的实验结果比较表明EOM-CCSD计算的价层垂直电离势整体上与SAC-CI结果相近,而优于OVGF和P3理论结果,在整个价层上,EOM-CCSD结果与实验值总体差距约0.2eV,在外价层这种差距相对较小,在内价层则有所增大.随基组增大EOM-CCSD计算得到的第一电离势与实验值差距迅速减小,约0.03eV.根据SAC-CI,OVGF,P3和EOM-CCSD对NF3和PF3计算结果,判断AsF3第一电离势约为12.8eV,而非12.3eV,同时给出AsF3的价层电离势依次为12.64,15.23,16.30,17.37,18.05,21.98eV.
The valence vertical potential (VIP) of XF3 (X = N, P, As) was systematically calculated by using EOM-CCSD and the symmetric matching cluster configuration interaction SAC-CI), outer layer Green’s function (OVGF) and partial third-order approximation (P3) have also been applied to the present calculation.Comparing with the existing experimental results, it is shown that the valence vertical ionization potential calculated by EOM- SAC-CI results are similar, but better than OVGF and P3 theoretical results, the overall EOM-CCSD results and the experimental value of the overall gap of about 0.2eV, in the outer price layer this gap is relatively small, there is the inner price layer The difference between the first ionization potential and the experimental value calculated with the increase of EOM-CCSD in the base group decreases rapidly, about 0.03eV. According to the calculation results of NF3 and PF3 by SAC-CI, OVGF, P3 and EOM-CCSD, The first ionization potential of AsF3 was determined to be about 12.8 eV instead of 12.3 eV, and the valence ionization potential of AsF3 was 12.64, 15.23, 16.30, 17.37, 18.05 and 21.98 eV, respectively.