Abstract
The size consistency of the second and third order energies of the multireference perturbation theory (Chen F, Davidson E, Iwata S. Int J Quant Chem, 2002, 86: 256) is investigated theoretically with a super-molecular model composed of N-hydrogen molecules separated by a large distance. It is found that the two perturbation series corresponding to two Hamiltonian partitions are not size consistent at the second and third order. However, two size consistent forms are suggested for two Hamiltonian partitions at the second order, if some approximations to the denominators of the original second order energies are assumed.
Similar content being viewed by others
References
Szabo A, Ostlund N S. Modern Quantum Chemistry. New York: Macmillan Publishing Company, 1982. 320–379
Bartlett R J. Many-body perturbation theory and coupled cluster theory for electron correlation in molecules. Ann Rev Phys Chem, 1981, 32: 359–401
Davidson E R, Jarzecki A A. Multi-reference perturbation theory. in: Hirao K ed. Recent Advances in Computational Chemistry. Vol 4. Singapore: World Scientific, 1999. 31–36
Chen F, Davidson E R, Iwata S. New time-independent perturbation theory for the multireference problem. Int J Quantum Chem, 2002, 86: 256–264
Brueckner K A. Many-body problem for strongly interacting particles. Phys Rev, 1955, 100: 36–45
Goldstone J. Derivation of the Brueckner many-body theory. Proc Roy Soc A, 1957, 239: 267–279
Witek H A, Nakano H, Hirao K. Multireference perturbation theory with optimized partitioning. J Chem Phys, 2003, 118: 8197–8206
Szabados A, Rolik z, Tóth G, Surján P R. Multiconfiguration perturbation theory: size consistency at second order. J Chem Phys, 2005, 122: 114104-1–114104-11
Rintelman J A, Adamovic I, Varganov S, Gordon MS. Multireference second order perturbation theory: how size consistent is “almost size consistent”. J Chem Phys, 2005, 122: 044105-1–044105-7
Luo F, Chen F, Chen C. Size consistency study on the single reference pertubation theory with two Hamiltonian partitions. Acta Phys-Chim Sin, 2006, 22: 1547–1550
Chen F, Davidson E R. Theoretical study of the electronic spectrum and ESR of the CH2OH radical. J Phys Chem A, 2001, 105: 4558–4562
Author information
Authors and Affiliations
Additional information
Supported by the National Natural Science Foundation of China (Grant No. 20473011), the University of Science and Technology Beijing (Grant No. 000074 14) and the Ministry of Education of China (Grant No. 11140036)
Rights and permissions
About this article
Cite this article
Chen, F. Theoretical study on the size consistency of the second and third order energies of the multireference perturbation theory. SCI CHINA SER B 50, 483–487 (2007). https://doi.org/10.1007/s11426-007-0074-0
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11426-007-0074-0