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用扩散蒙特卡罗方法研究BH2, B(OH)2, BCl2和BCl的键离解能
引用本文:李会然,程新路,张红.用扩散蒙特卡罗方法研究BH2, B(OH)2, BCl2和BCl的键离解能[J].化学物理学报,2012,25(1):65-69.
作者姓名:李会然  程新路  张红
作者单位:四川大学原子与分子物理研究所,成都610065;四川大学原子与分子物理研究所,成都610065;四川大学原子与分子物理研究所,成都610065;四川大学物理科学与技术学院,成都610065
摘    要:采用扩散蒙特卡罗(DMC)方法计算了BH2, B(OH)2, BCl2和BCl的HB-H和HOB-OH的键离解能, 同时也研究了轨道选择和Backflow变换对DMC计算结果的影响. 在Slater-Jastrow DMC(SJ-DMC)计算方法中,当采用B3PW91轨道时得到的HB-H和HOB-OH键离解能分别是359.1±0.12和98.2±0.12 kJ/mol;用B3LYP SJ-DMC计算键离解能得到了与用B3PW91 SJ-DMC方法类似的结果.通过BF-DMC(即在DMC中引入backflow修正)计算得到的HB?H键离解能为369.6±0.12 kJ/mol,也得到了更加接近实验值的HOB-OH键离解能为446.0±1.84 kJ/mol.由DMC的计算结果可以断定HB?H的键离解能的实验值为375.8 kJ/mol.另外还给出了BCl2和BCl的键离解能的计算结果.

关 键 词:键离解能,扩散蒙特卡罗方法,轨道选择,Backflow变换
收稿时间:2011/10/31 0:00:00

Diffusion Monte Carlo Study of Bond Dissociation Energies for BH2, B(OH)2, BCl2, and BCl
Hui-ran Li,Xin-lu Cheng and Hong Zhang.Diffusion Monte Carlo Study of Bond Dissociation Energies for BH2, B(OH)2, BCl2, and BCl[J].Chinese Journal of Chemical Physics,2012,25(1):65-69.
Authors:Hui-ran Li  Xin-lu Cheng and Hong Zhang
Abstract:On basis of bond dissociation energies (BDEs) for BH2, B(OH)2, BCl2, and BCl, the diffusion Monte Carlo (DMC) method is applied to explore the BDEs of HB-H, HOB-OH, ClB-Cl, and B-Cl. The effect of the choice of orbitals, as well as the backflow transformation, is studied. The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB?H, 410.5±0.50 kJ/mol for HOB-OH, 357.8±1.46 kJ/mol for ClB-Cl, and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used. DMC with backflow corrections (BF-DMC) gives a HB-H BDE of 369.9±0.12 kJ/mol which is close to one of the available experimental value (375.8 kJ/mol). In the case of HOB-OH BDE, the BF-DMC calculation is 446.0±1.84 kJ/mol that is closer to the experimental BDE. The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol, which are close to the experimental BDEs, 341.9 and 530.0 kJ/mol, respectively.
Keywords:Bond dissociation energy  Diffusion Monte Carlo method  Choice of orbitals  Backflow transformation
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