Implementation of Analytical Energy Gradient of Spin-Dependent General Hartree-Fock Method Based on the Infinite-Order Douglas-Kroll-Hess Relativistic Hamiltonian with Local Unitary Transformation

Yuya Nakajima, Junji Seino, Hiromi Nakai

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.

Original languageEnglish
Pages (from-to)2181-2190
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume12
Issue number5
DOIs
Publication statusPublished - 2016 May 10

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Hamiltonians
gradients
Molecules
Gradient methods
Iridium
Silver
energy
heavy elements
relativistic effects
iridium
diatomic molecules
Atoms
Geometry
silver
geometry
atoms
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

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title = "Implementation of Analytical Energy Gradient of Spin-Dependent General Hartree-Fock Method Based on the Infinite-Order Douglas-Kroll-Hess Relativistic Hamiltonian with Local Unitary Transformation",
abstract = "An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.",
author = "Yuya Nakajima and Junji Seino and Hiromi Nakai",
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T1 - Implementation of Analytical Energy Gradient of Spin-Dependent General Hartree-Fock Method Based on the Infinite-Order Douglas-Kroll-Hess Relativistic Hamiltonian with Local Unitary Transformation

AU - Nakajima, Yuya

AU - Seino, Junji

AU - Nakai, Hiromi

PY - 2016/5/10

Y1 - 2016/5/10

N2 - An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.

AB - An analytical energy gradient for the spin-dependent general Hartree-Fock method based on the infinite-order Douglas-Kroll-Hess (IODKH) method was developed. To treat realistic systems, the local unitary transformation (LUT) scheme was employed both in energy and energy gradient calculations. The present energy gradient method was numerically assessed to investigate the accuracy in several diatomic molecules containing fifth- and sixth-period elements and to examine the efficiency in one-, two-, and three-dimensional silver clusters. To arrive at a practical calculation, we also determined the geometrical parameters of fac-tris(2-phenylpyridine)iridium and investigated the efficiency. The numerical results confirmed that the present method describes a highly accurate relativistic effect with high efficiency. The present method can be a powerful scheme for determining geometries of large molecules, including heavy-element atoms.

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