物理化学学报 >> 1996, Vol. 12 >> Issue (02): 97-101.doi: 10.3866/PKU.WHXB19960201

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O-3激发态电子结构及内部电荷转移理论研究

曹泽星,黄宏新,田安民   

  1. 湖南师范大学化学系，长沙 410081|四川联合大学化学系，成都 610064
  • 收稿日期:1995-10-20 修回日期:1995-12-04 发布日期:1996-02-15
  • 通讯作者:

Theoretical Studies of the Excited States and Intra-ionic Charge Transfer of O-3

Cao Ze-Xing,Huang Hong-Xin,Tian An-Min   

  1. Department of Chemistry,Hunan Normal University,Changsha 410081|Department of Chemistry,Sichuan United University,Chengdu 610064
  • Received:1995-10-20 Revised:1995-12-04 Published:1996-02-15
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关键词: O-3;激发态电子结构, 电荷转移, Ab initio计算

Abstract:

The optimized geometries, energies and harmonic vibrational frequencies of the doublet and quadruplet electronic states of O3- are theoretically predicted at the UHF/631+G*, MCSCF and CISD/MCSCF level. The geometry of the ground has Cs syrnmetry, and bond lengths of 1. 369 and 1.350Å, and a bond angle of 115.7° at the MCSCF level. The excitation energies for transitions 2A2←X2A", 2A’←X 2A" and 2B2← X 2A"I are 2.648, 1.372 and 1 .463 eV, respectively. For the quadruplet states of the ozonide anion the van der Waals complexes only are found. The intra-ionic charge transfers for the X2A", 2A’ and 4∑- states are investigated. The reactions 2A"→2B2→2A",2A’→ 2A1→2A’ and 4∑-→4∑g→4∑- have activation barriers of 1.281, 13.344 and 81.484 kcal﹒mol-1, and rate constants of 3.254×1011 ,4.688×102 and 2.653×10-49 s-1, respectively.

Key words: O-3, Electronic structures of the excited state, Charge transfer, Ab initio calculations