后哈特里－福克方法

在计算化学中，后哈特里－福克方法（英语：post-Hartree–Fock）[1][2]是对哈特里－福克方法（HF）或自洽场方法（SCF）加以改进而发展的一系列方法。这些方法增加了电子耦合项，更准确地考虑了电子间的排斥；而在哈特里－福克方法中，排斥力仅为平均数。

细节

SCF程序对多体薛定谔方程的性质及其解集做出了几点假设：

  • 对于分子，假定玻恩–奥本海默近似，波函数应当是每个原子核坐标的函数。
  • 通常情况下，完全忽略狭义相对论效应，动量算符被假定为完全非相对论的。
  • 基组由有限数量的正交函数组成，波函数是完备（无限）基组中函数的线性组合。
  • 能量本征函数被假定为单电子波函数的乘积；除了因波函数的反对称性而产生的交换能量外，电子校正效应均被忽略。

对于绝大多数体系而言，特别是对于激发态及其反应（例如分子解离反应），第四项是最重要的。因此，术语“后哈特里－福克方法”常用于电子校正的近似方法。

通常情况下，后哈特里－福克方法比哈特里－福克方法更加准确，但是需要消耗更多的计算资源。

方法

相关方法

使用多个行列式的方法并非严格的后哈特里－福克方法，因为它们使用单​​个行列式作为参考，但是它们经常使用类似的扰动或构型相互作用方法来改进电子耦合效应的描述。这些方法包括：

参考文献

  1. ^ Cramer, Christopher J. Essentials of Computational Chemistry. John Wiley & Sons. 2002. ISBN 0-470-09182-7. 
  2. ^ Jensen, Frank. Introduction to Computational Chemistry 2nd edition. John Wiley & Sons. 1999. ISBN 0-470-01187-4. 
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  4. ^ Martin Head-Gordon; Rudolph J. Rico; Manabu Oumi & Timothy J. Lee. A doubles correction to electronic excited states from configuration interaction in the space of single substitutions. Chemical Physics Letters (Elsevier). 1994, 219 (1–2): 21–29. Bibcode:1994CPL...219...21H. doi:10.1016/0009-2614(94)00070-0. 
  5. ^ George D. Purvis & Rodney J. Bartlett. A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples. The Journal of Chemical Physics (The American Institute of Physics). 1982, 76 (4): 1910–1919. Bibcode:1982JChPh..76.1910P. doi:10.1063/1.443164. 
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  7. ^ Troy Van Voorhis & Martin Head-Gordon. Two-body coupled cluster expansions. The Journal of Chemical Physics (The American Institute of Physics). June 19, 2001, 115 (11): 5033–5041. Bibcode:2001JChPh.115.5033V. doi:10.1063/1.1390516. 
  8. ^ H. D. Meyer; U. Manthe & L. S. Cederbaum. The multi-configurational time-dependent Hartree approach. Chem. Phys. Lett. 1990, 165 (73). doi:10.1016/0009-2614(90)87014-I. 
  9. ^ Chr. Møller & M. S. Plesset. Note on an Approximation Treatment form Many-Electron Systems. Physical Review (The American Physical Society). October 1934, 46 (7): 618–622. Bibcode:1934PhRv...46..618M. doi:10.1103/PhysRev.46.618. 
  10. ^ Krishnan Raghavachari & John A. Pople. Approximate fourth-order perturbation theory of the electron correlation energy. International Journal of Quantum Chemistry (Wiley InterScience). February 22, 1978, 14 (1): 91–100. doi:10.1002/qua.560140109. 
  11. ^ John A. Pople; Martin Head‐Gordon & Krishnan Raghavachari. Quadratic configuration interaction. A general technique for determining electron correlation energies. The Journal of Chemical Physics (American Institute of Physics). 1987, 87 (10): 5968–35975. Bibcode:1987JChPh..87.5968P. doi:10.1063/1.453520. 
  12. ^ Larry A. Curtiss; Krishnan Raghavachari; Gary W. Trucks & John A. Pople. Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds. The Journal of Chemical Physics (The American Institute of Physics). February 15, 1991, 94 (11): 7221–7231. Bibcode:1991JChPh..94.7221C. doi:10.1063/1.460205. 
  13. ^ Larry A. Curtiss; Krishnan Raghavachari; Paul C. Redfern; Vitaly Rassolov & John A. Pople. Gaussian-3 (G3) theory for molecules containing first and second-row atoms. The Journal of Chemical Physics (The American Institute of Physics). July 22, 1998, 109 (18): 7764–7776. Bibcode:1998JChPh.109.7764C. doi:10.1063/1.477422. 
  14. ^ William S. Ohlinger; Philip E. Klunzinger; Bernard J. Deppmeier & Warren J. Hehre. Efficient Calculation of Heats of Formation. The Journal of Physical Chemistry A (ACS Publications). January 2009, 113 (10): 2165–2175. PMID 19222177. doi:10.1021/jp810144q. 

进一步阅读

  • Jensen, F. Introduction to Computational Chemistry. New York: John Wiley & Sons. 1999. ISBN 0471980854.