物理化学学报 >> 2006, Vol. 22 >> Issue (03): 265-269.doi: 10.3866/PKU.WHXB20060302

研究论文 上一篇    下一篇

Au+(1S, 3D)与N2O(1Σ+)反应机理的理论研究

吕玲玲; 王永成   

  1. 天水师范学院生命科学与化学学院, 甘肃 天水 741000; 西北师范大学化学化工学院, 兰州 730070
  • 收稿日期:2005-08-08 修回日期:2005-09-22 发布日期:2006-03-10
  • 通讯作者: 吕玲玲 E-mail:lvling100@163.com

Theoretical Studies on the Reaction Mechanism of Au+(1S, 3D) and N2O(1Σ+)

LÜ Ling-Ling; WANG Yong-Cheng   

  1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741000, P. R. China; College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China
  • Received:2005-08-08 Revised:2005-09-22 Published:2006-03-10
  • Contact: LÜ Ling-Ling E-mail:lvling100@163.com

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(1Σ+)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)+ N2O(1Σ+)→1NA-Complex-1→1NA-TS1→1NA-Complex-2→1NA-Crossing→[3OAuNN]+和Au+(1S)+ N2O(1Σ+)→1NB-Complex→1NB-Crossing→[AuNN(1Σ+)]++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.

关键词: Au+(1S, 3D), N2O(1Σ+), 密度泛函理论, 反应机理, 系间窜越

Abstract: The reaction of Au+(1S, 3D) ions with N2O(1Σ+) 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(1Σ+)→1NA-Complex-1→1NA-TS1→1NA-Complex-2→ 1NA-Crossing→[3OAuNN]+ and Au+(1S) + N2O(1Σ+) →1NB-Complex →1NB-Crossing →[AuNN(1Σ+)]+ + 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.

Key words: Au+(1S, 3D), N2O(1Σ+), Density functional theory, Reaction mechanism, Intersystem crossing