XF_3(X=N,P,As)分子价层电离势的三阶代数图-表构建法计算

Calculations of valence shells ionization potentials of XF_3(X=N,P,As)using the third-order algebraic diagrammatic construction scheme

应用三阶代数图-表构建法（third-order algebraic diagrammatic construction scheme 简写为 ADC （3））计算了XF3（X=N,P,As）的价层垂直电离势（VIP）.结果表明：内壳层电子关联对电离主峰位置影响非常小；来自不同理论结果的分子结构对电离主峰位置有较小影响；基组差异则表现的非常明显.由计算值和实验结果比较可知：在实验分子结构和 cc-pVDZ基组下,应用 ADC（3）得到的电离势与实验值整体上差距最小；ADC（3）计算的第一电离势往往小于实验值约0.4～0.8 eV,其余主峰位置与实验值差距约0.01～0.3 eV；随基组增大,ADC（3）结果与实验值偏差明显增大.因此,利用 ADC（3）方法计算价层电离势时,建议使用价层电子关联,基组则采用 cc-pVDZ或DZP,结构除采用实验外也可直接从耦合簇、密度泛函等理论获得.

The valence shell vertical ionization potentials （VIP）of XF3 （X=N,P,As）have been calcu-lated by the third-order algebraic diagrammatic construction scheme method （ADC（3））.It shows that inner shell electrons almost have no effect and the structures from different theory levels have a little effect on the location of the main peaks,but significant differences are found when the different basis sets are adopted.The differences between calculation and experimental results are founded to be the smallest with the cc-pVDZ basis set combining with experimental structures.The first ionization poten-tial is 0.4～0.8 eV smaller than experimental value,the differences of other main peaks are about 0.01～0.3 eV,while the ADC（3）value clearly becomes larger with increasing of basis sets.Above all,the experimental structure combined with cc-pVDZ basis set is the best choice for the calculation of the va-lence shell ionization potentials by ADC（3）method.