@article{oai:nagoya.repo.nii.ac.jp:00007064,
author = {Yasuda, Koji and Yamaki, Daisuke},
issue = {9},
journal = {JOURNAL OF CHEMICAL PHYSICS},
month = {Sep},
note = {We propose a minimum principle to derive a QM/MM (quantum-mechanical/molecular-mechanical) method from the first principle. We approximate the Hamiltonian of a spectator substituent as the structure-dependent effective Hamiltonian in a least-squares sense. This effective Hamiltonian is expanded with the orthogonal operator set called the normal-ordered product. We determine the structure-dependent energy that corresponds to the classical MM energy and the extra one-electron potential that takes account of the interface effects. This QM/MM method is free from the double-counting problem and the artificial truncation of the localized molecular orbitals. As a numerical example we determine the one-electron effective Hamiltonian of the methyl group. This effective Hamiltonian is applied to the ethane and CH3CH2X molecules (X=CH_3, NH_2 , OH, F, COOH, NH^＋_3 , OH^＋_2 , and COO^-). It reproduced the relative energies, potential energy curves, and the Mulliken populations of the all-electron calculations fairly well.},
pages = {3964--3972},
title = {Simple minimum principle to derive a quantum-mechanical/molecular-mechanical method},
volume = {121},
year = {2004}
}