TY - JOUR
T1 - The influence of correlation on the interpretation of Hund's multiplicity rule
T2 - A quantum Monte Carlo study
AU - Oyamada, Takayuki
AU - Hongo, Kenta
AU - Kawazoe, Yoshiyuki
AU - Yasuhara, Hiroshi
PY - 2006
Y1 - 2006
N2 - A systematic quantum Monte Carlo study of 2p atoms (C, N, O) and 3p atoms (Si, P, S) is performed to investigate the influence of correlation on the interpretation of Hund's multiplicity rule, which is an extension of our previous study of the carbon atom [J. Chem. Phys. 121, 7144 (2004)] to heavier atoms. The accuracy in the present study is significantly improved as compared with the previous study. A detailed analysis of the correlation contribution to individual energy components of the total energy is given beyond the self-consistent Hartree-Fock calculation. The stability of the highest spin-multiplicity state of all the atoms is ascribed to the greater electron-nucleus attraction energy that is gained at the cost of increasing the electron-electron repulsion energy as well as the kinetic energy. The present study demonstrates that correlation does not change the above conclusion due to the Hartree-Fock theory to support Boyd's less screening mechanism.
AB - A systematic quantum Monte Carlo study of 2p atoms (C, N, O) and 3p atoms (Si, P, S) is performed to investigate the influence of correlation on the interpretation of Hund's multiplicity rule, which is an extension of our previous study of the carbon atom [J. Chem. Phys. 121, 7144 (2004)] to heavier atoms. The accuracy in the present study is significantly improved as compared with the previous study. A detailed analysis of the correlation contribution to individual energy components of the total energy is given beyond the self-consistent Hartree-Fock calculation. The stability of the highest spin-multiplicity state of all the atoms is ascribed to the greater electron-nucleus attraction energy that is gained at the cost of increasing the electron-electron repulsion energy as well as the kinetic energy. The present study demonstrates that correlation does not change the above conclusion due to the Hartree-Fock theory to support Boyd's less screening mechanism.
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U2 - 10.1063/1.2209692
DO - 10.1063/1.2209692
M3 - Article
AN - SCOPUS:33745792755
SN - 0021-9606
VL - 125
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 1
M1 - 014101
ER -