Open Access
Subscription Access
Transition Probability Approach for Direct Calculation of Coefficients of Configuration Interaction Wave Function
To reduce the computation cost of configuration interaction (CI) method, a novel technique is used to calculate the coefficients of doubly excited determinants directly from orbital energies, orbital overlap matrix and electron population obtained from Hartree–Fock level run. This approach to approximate the coefficients of CI wave function is termed as transition probability approximated CI (TPA-CI). In principle, calculated dynamical electron correlation energies of TPA-CI and full CI (FCI) are equivalent. It is observed that computed TPA-CI correlation energies of hydrogen, water, ammonia and ozone are close to the FCI values, within 5% error. The potential energy curve of hydrogen molecule is also studied, and it is found that the energy is minimum at its equilibrium bond length.
Keywords
Configuration Interaction, Potential Energy Curve, Transition Probability Approximation, Wave Function.
User
Font Size
Information
- Fock, V., Naherungsmethode zur Losung des quantenmechanischen Mehrkorperproblems. Z. Physik., 1930, 61, 126–148.
- Pauli, W., Uber den Zusammenhang des Abschlusses der Elektronengruppen im Atom mit der Komplexstruktur der Spektr. Z. Physik., 1925, 31, 756–783.
- Boys, S. F., Electronic wave functions II. A calculation for the ground state of the beryllium atom. Proc. R. Soc. London, Ser. A, 1950, 201, 125–137.
- Pople, J. A. and Binkley, J. S., Theoretical models incorporating electron correlation. Int. J. Quant. Chem. Symp., 1976, 10, 1–19.
- Cizek, J., On the correlation problem in atomic and molecular systems. Calculation of wave function components in Ursell-type expansion using quantum-field theoretical methods. J. Chem. Phys., 1966, 45, 4256–4266.
- Cizek, J., On the use of the cluster expansion and the technique of diagrams in calculations of correlation effects in atoms and molecules. Adv. Chem. Phys., 1969, 14, 35–89.
- Purvis, D. and Bartlett, R. J., A full coupled-cluster singles and doubles model: the inclusion of disconnected triples. J. Chem. Phys. 1982, 76, 1910–1918.
- Moller, C. and Plasset, M. S., Note on an approximation treatment for many-electron systems. Phys. Rev., 1934, 46, 618.
- Leininger, M. L., Allen, W. D., Schaefer, H. F. and Sherrill, C. D., Is MoIler–Plesset perturbation theory a convergent ab initio method? J. Chem. Phys., 2000, 112, 9213–9222.
- Bag, A., Manohar, P. U., Vaval, N. and Pal, S., First- and second-order electrical properties computed at the FSMRCCSD level for excited states of closed-shell molecules using the constrained-variational approach. J. Chem. Phys., 2009, 131, 024102.
- Bag, A., Manohar, P. U. and Pal, S., Analytical dipole moments and dipole polarizabilities of oxygen mono-fluoride and nitrogen dioxide: a constrained variational response to Fock-Space multi-reference coupled-cluster method. Comput. Lett., 2007, 3, 351(2–4).
- Manohar, P. U., Shamasundar, K. R., Bag, A., Vaval, N. and Pal, S., On some aspects of Fock-space multi-reference coupled-cluster singles and doubles energies and optical properties. In Challenges and Advances in Computational Chemistry and Physics, 2010, vol. 11, pp. 375–393.
- Bag, A., Bhattacharya, S. and Pal, S., Static hyper-polarizability of open shell molecules computed at the FSMRCCSD level using constrained variational approach. In Recent Advances in Spectroscopy: Theoretical, Astrophysical and Experimental Perspectives (ed. Chaudhury, R. K. et al.), 2010, p. 99–109.
- Bag, A., Linear Response Approach in FSMRCC for Molecular Property, LAMBERT Academic Publishing, Deutschland, Germany, 2016.
- GAMESS, General atomic and molecular electronic structure system. J. Comput. Chem., 1993, 14, 1347–1363.
- Kolos, W. and Wolniewicz, L., Improved theoretical ground-state energy of the hydrogen molecule. J. Chem. Phys., 1968, 49, 404–410.
Abstract Views: 350
PDF Views: 125