Citation: CAO Jing-Si, CHEN Fei-Wu. Fitting and Extrapolation of Configuration Interaction Energies in Complete Active Space[J]. Acta Physico-Chimica Sinica, ;2017, 33(6): 1130-1139. doi: 10.3866/PKU.WHXB201703221 shu

Fitting and Extrapolation of Configuration Interaction Energies in Complete Active Space

CAO Jing-Si ,
CHEN Fei-Wu

Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing;Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Beijing 100083, P. R. China

Received Date: 2 December 2016
Revised Date: 27 February 2017

Fund Project: The project was supported by the National Natural Science Foundation of China (21173020, 21473008).

Configuration interaction calculation in complete active space is related to the numbers of active electrons and orbitals. However, configuration interaction energy is not a monotonically decreasing function of these two variables. Thus, the numbers of active electrons and orbitals are not proper variables to extrapolate the configuration interaction energy. In order to address this problem, we defined a new variable:maximum number of unoccupied orbitals in the complete active space. We performed a series of configuration interaction calculations on singlet, doublet, and triplet molecules, and simulated their ground state energies with the number of active electrons and the number of maximum unoccupied orbitals. The mean square root errors of these simulations were on the order of 10^-6. The accuracy of the extrapolated energies was better than that of MP4 and than that of CCSD for small molecules. The extrapolated full configuration interaction energies were very close to the energy values of full configuration interactions. Furthermore, the extrapolated energies were exploited to optimize the bond distances of several diatomic molecules and to compute harmonic vibrational frequencies. Their accuracies were better than that of the complete active space self-consistent field.
- Complete active space,
- Active electron,
- Active orbital,
- Energy extrapolation,
- Bond length,
- Harmonic vibrational frequency
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