Reconsidering an analytical gradient expression within a divide-and-conquer self-consistent field approach: Exact formula and its approximate treatment

Masato Kobayashi, Tomotaka Kunisada, Tomoko Akama, Daisuke Sakura, Hiromi Nakai

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

An analytical energy gradient formula for the density-matrix-based linear-scaling divide-and-conquer (DC) self-consistent field (SCF) method was proposed in a previous paper by Yang and Lee (YL) [J. Chem. Phys. 103, 5674 (1995)]. Since the formula by YL does not correspond to the exact gradient of the DC-SCF energy, we derive the exact formula by direct differentiation, which requires solving the coupled-perturbed equations while including the inter-subsystem coupling terms. Next, we present an alternative formula for approximately evaluating the DC-SCF energy gradient, assuming the variational condition for the subsystem density matrices. Numerical assessments confirmed that the DC-SCF energy gradient values obtained by the present formula are in reasonable agreement with the conventional SCF values when adopting a reliable buffer region. Furthermore, the performance of the present method was found to be better than that of the YL method.

Original languageEnglish
Article number034105
JournalJournal of Chemical Physics
Volume134
Issue number3
DOIs
Publication statusPublished - 2011 Jan 21

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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