原子与分子物理学报
原子與分子物理學報
원자여분자물이학보
CHINESE JOURNAL OF ATOMIC AND MOLECULAR PHYSICS
2014年
4期
515-520
,共6页
XF3 (X=N,P,As)%价层垂直电离势%三阶代数图-表构建法
XF3 (X=N,P,As)%價層垂直電離勢%三階代數圖-錶構建法
XF3 (X=N,P,As)%개층수직전리세%삼계대수도-표구건법
XF3 (X=N,P,As)%Valence shell vertical ionization potential%ADC(3)
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.
應用三階代數圖-錶構建法(third-order algebraic diagrammatic construction scheme 簡寫為 ADC (3))計算瞭XF3(X=N,P,As)的價層垂直電離勢(VIP).結果錶明：內殼層電子關聯對電離主峰位置影響非常小；來自不同理論結果的分子結構對電離主峰位置有較小影響；基組差異則錶現的非常明顯.由計算值和實驗結果比較可知：在實驗分子結構和 cc-pVDZ基組下,應用 ADC(3)得到的電離勢與實驗值整體上差距最小；ADC(3)計算的第一電離勢往往小于實驗值約0.4~0.8 eV,其餘主峰位置與實驗值差距約0.01~0.3 eV；隨基組增大,ADC(3)結果與實驗值偏差明顯增大.因此,利用 ADC(3)方法計算價層電離勢時,建議使用價層電子關聯,基組則採用 cc-pVDZ或DZP,結構除採用實驗外也可直接從耦閤簇、密度汎函等理論穫得.
응용삼계대수도-표구건법(third-order algebraic diagrammatic construction scheme 간사위 ADC (3))계산료XF3(X=N,P,As)적개층수직전리세(VIP).결과표명：내각층전자관련대전리주봉위치영향비상소；래자불동이론결과적분자결구대전리주봉위치유교소영향；기조차이칙표현적비상명현.유계산치화실험결과비교가지：재실험분자결구화 cc-pVDZ기조하,응용 ADC(3)득도적전리세여실험치정체상차거최소；ADC(3)계산적제일전리세왕왕소우실험치약0.4~0.8 eV,기여주봉위치여실험치차거약0.01~0.3 eV；수기조증대,ADC(3)결과여실험치편차명현증대.인차,이용 ADC(3)방법계산개층전리세시,건의사용개층전자관련,기조칙채용 cc-pVDZ혹DZP,결구제채용실험외야가직접종우합족、밀도범함등이론획득.
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.
