Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Moller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H 4)3P}2(C6H5)Pt(C≡C) 4Pt(C6H5){(p-CH3C6H 4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.

Original languageEnglish
Article number034109
JournalJournal of Chemical Physics
Volume139
Issue number3
DOIs
Publication statusPublished - 2013

Fingerprint

Electron correlations
relativistic effects
scalars
Molecules
Coinage
scaling
molecules
Hamiltonians
electrons
Correlation methods
Platinum
halides
Hydrogen
platinum
Metals
costs
hydrogen
metals
excitation
Costs

ASJC Scopus subject areas

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

Cite this

@article{1b84a42bc2b64d9cbef4ecd1682cc6d2,
title = "Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules",
abstract = "In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Moller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H 4)3P}2(C6H5)Pt(C≡C) 4Pt(C6H5){(p-CH3C6H 4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.",
author = "Junji Seino and Hiromi Nakai",
year = "2013",
doi = "10.1063/1.4813595",
language = "English",
volume = "139",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "3",

}

TY - JOUR

T1 - Local unitary transformation method toward practical electron correlation calculations with scalar relativistic effect in large-scale molecules

AU - Seino, Junji

AU - Nakai, Hiromi

PY - 2013

Y1 - 2013

N2 - In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Moller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H 4)3P}2(C6H5)Pt(C≡C) 4Pt(C6H5){(p-CH3C6H 4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.

AB - In order to perform practical electron correlation calculations, the local unitary transformation (LUT) scheme at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level [J. Seino and H. Nakai, J. Chem. Phys. 136, 244102 (2012); and ibid. 137, 144101 (2012)], which is based on the locality of relativistic effects, has been combined with the linear-scaling divide-and-conquer (DC)-based Hartree-Fock (HF) and electron correlation methods, such as the second-order Moller-Plesset (MP2) and the coupled cluster theories with single and double excitations (CCSD). Numerical applications in hydrogen halide molecules, (HX)n (X = F, Cl, Br, and I), coinage metal chain systems, Mn (M = Cu and Ag), and platinum-terminated polyynediyl chain, trans,trans-{(p-CH3C6H 4)3P}2(C6H5)Pt(C≡C) 4Pt(C6H5){(p-CH3C6H 4)3P}2, clarified that the present methods, namely DC-HF, MP2, and CCSD with the LUT-IODKH Hamiltonian, reproduce the results obtained using conventional methods with small computational costs. The combination of both LUT and DC techniques could be the first approach that achieves overall quasi-linear-scaling with a small prefactor for relativistic electron correlation calculations.

UR - http://www.scopus.com/inward/record.url?scp=84903362058&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84903362058&partnerID=8YFLogxK

U2 - 10.1063/1.4813595

DO - 10.1063/1.4813595

M3 - Article

AN - SCOPUS:84903362058

VL - 139

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 3

M1 - 034109

ER -