Quantum Monte Carlo study of porphyrin transition metal complexes.

Quantum Chemistry Division, Graduate School of Science, Yokohama City University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027, Japan.
The Journal of Chemical Physics (Impact Factor: 3.12). 09/2008; 129(8):085103. DOI: 10.1063/1.2966003
Source: PubMed

ABSTRACT Diffusion quantum Monte Carlo (DMC) calculations for transition metal (M) porphyrin complexes (MPo, M=Ni,Cu,Zn) are reported. We calculate the binding energies of the transition metal atoms to the porphin molecule. Our DMC results are in reasonable agreement with those obtained from density functional theory calculations using the B3LYP hybrid exchange-correlation functional. Our study shows that such calculations are feasible with the DMC method.

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    ABSTRACT: A projector Monte Carlo method based on Slater determinants (PMC-SD) is expanded to excited state calculations. Target excited states are calculated state-by-state by eliminating the components of the lower states from the imaginary-time propagator. Test calculations are performed for the singlet excited states of H2O and LiF. As the calculations of H2O show, the accuracy of the PMC-SD method is improved systematically by increasing the number of walkers. The full-CI energies are obtainable as a limit for a given basis set. The avoided crossing of covalent and ionic states in the dissociation of LiF is well reproduced using the PMC-SD method.
    Chemical Physics Letters 01/2010; 485:367-370. · 2.15 Impact Factor


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May 21, 2014