摘要
采用密度泛函B3LYP方法,O和N用6-311+G*基组,Au+用赝势基组(8s7p6d)/[6s5p3d],研究了Au+(~1S,~3D)离子和N2O(~1∑^+)分子的反应机理.报道了在基态单重态和激发三重态势能面上各反应物、中间体和过渡态的构型特征及能量.结果表明,两个主反应通道Au+(1S)+N_2O(~1∑^+)→1NA-Complex-1→1NA-TS1→1NA-Complex-2→1NA-Crossing→[3OAuNN]+和Au+(1S)+N2O(~1∑^+)→1NB-Complex→1NB-Crossing→[AuNN(1∑+)]++O(3P)都需经过反应交叉势能面,出现“系间窜越”.用内禀坐标单点计算垂直激发态的方法确定了势能面交叉点,并用含时密度泛函TD-B3LYP方法进一步探讨了自旋翻转机理.
The reaction of Au^＋（^1S, 3D） ions with N2O（^1∑^＋） are studied by means of B3LYP/6-311＋G^＊（the basis set of Au^＋ is （8s7p6d）/[6s5p3d]）. The structures of all reactants, products, complexes, and transition structure have been optimized and characterized at the fundamental singlet and excited triplet electronic states. The calculated results show that two main reaction pathways Au^＋（^1S）＋N2O（^1∑^＋）→^1NA-Complex-1→^1NA-TS1→^1NA-Complex-2→^1NA-Crossing→[^3OAuNN]^＋ and Au^＋（^1S）＋N2O（^1∑^＋）→^1NB-Complex→^1NB-Crossing→[AuNN（^1∑^＋）]^＋＋O（^3P） must proceed through a crossing point of the singlet and triplet surfaces and appear as ＂intersystem crossing＂. Crossing points are located by means of the intrinsic reaction coordinate single point vertical excited approach. The mechanisms of spin inversion are discussed.
出处
《物理化学学报》
SCIE
CAS
CSCD
北大核心
2006年第3期265-269,共5页
Acta Physico-Chimica Sinica
基金
甘肃省教育厅基金(021-22)资助项目
