中国科学院研究生院学报
中國科學院研究生院學報
중국과학원연구생원학보
JOURNAL OF THE GRADUATE SCHOOL OF THE CHINESE ACADEMY OF SCIENCES
2011年
4期
448-456
,共9页
C6H5CN+离子%CASPT2%光解离
C6H5CN+離子%CASPT2%光解離
C6H5CN+리자%CASPT2%광해리
C6H5CN+ ion%CASPT2%photodissociation
使用完全活化空间自洽场(CASSCF)和多组态的二级微扰理论(CASPT2)方法,对C6H5CN+离子去CN的光解离反应进行了研究.计算了12B1,12A2,12B2,22B1和12A1电子态的去CN解离势能曲线.通过对渐近产物的能量、构型、电荷和自旋密度布居的分析,得出结论:12A1,12B1,12A2,22B1和12B2的解离产物分别为C6H5+ (X1A1)+CN(X2∑+)（第1解离限）,C6H5+(1 3B1)+CN(X2∑+)（第2解离限）,C6H5 (11A2)+CN(X2∑+)（第3解离限）,C6H5+ (11B1)+CN（X2Σ+）（第4解离限）和C6H5+ (X1A1)+CN(12(Ⅱ))（第5解离限）.
使用完全活化空間自洽場(CASSCF)和多組態的二級微擾理論(CASPT2)方法,對C6H5CN+離子去CN的光解離反應進行瞭研究.計算瞭12B1,12A2,12B2,22B1和12A1電子態的去CN解離勢能麯線.通過對漸近產物的能量、構型、電荷和自鏇密度佈居的分析,得齣結論:12A1,12B1,12A2,22B1和12B2的解離產物分彆為C6H5+ (X1A1)+CN(X2∑+)（第1解離限）,C6H5+(1 3B1)+CN(X2∑+)（第2解離限）,C6H5 (11A2)+CN(X2∑+)（第3解離限）,C6H5+ (11B1)+CN（X2Σ+）（第4解離限）和C6H5+ (X1A1)+CN(12(Ⅱ))（第5解離限）.
사용완전활화공간자흡장(CASSCF)화다조태적이급미우이론(CASPT2)방법,대C6H5CN+리자거CN적광해리반응진행료연구.계산료12B1,12A2,12B2,22B1화12A1전자태적거CN해리세능곡선.통과대점근산물적능량、구형、전하화자선밀도포거적분석,득출결론:12A1,12B1,12A2,22B1화12B2적해리산물분별위C6H5+ (X1A1)+CN(X2∑+)（제1해리한）,C6H5+(1 3B1)+CN(X2∑+)（제2해리한）,C6H5 (11A2)+CN(X2∑+)（제3해리한）,C6H5+ (11B1)+CN（X2Σ+）（제4해리한）화C6H5+ (X1A1)+CN(12(Ⅱ))（제5해리한）.
CN-loss photodissociation of the C6H5CN + ion has been studied within the C2v symmetry using CASSCF and CASPT2 methods.The CASPT2//CASSCF dissociation potential energy curves (PECs) for the five lowest-lying states were calculated.By checking the relative energies,the fragmental geometries,and the charge and spin density populations of the asymptote products along the PECs,we conclude that the 12A1,12B1,12A2,22B1,and 12B2 states of C6H5CN+ correlate with C6H5+ (X1A1) + CN (X2Σ+),C6H5+ (13B1) + CN (X2Σ+),C6H5+ (11A2) +CN (X2Σ+),C6H5+(11B1) + CN (X2Σ+),and C6H5+ (X1A1) + CN (12(II)),which are the first,second,third,fourth,and fifth dissociation limits,respectively.
