TY - CHAP

T1 - A Linear-Scaling Divide-and-Conquer Quantum Chemical Method for Open-Shell Systems and Excited States

AU - Yoshikawa, Takeshi

AU - Nakai, Hiromi

N1 - Publisher Copyright:
© 2017 John Wiley & Sons, Ltd. All rights reserved.

PY - 2017/6/21

Y1 - 2017/6/21

N2 - The acceleration of ab initio electronic structure calculations has been one of the most important themes in the field of quantum chemistry since the mid-1980s when a series of single-reference theories starting from the Hartree-Fock (HF) method were already mature. The standard single-reference quantum chemical calculations consist of three time-consuming steps, namely, the Fock-matrix construction, its diagonalization to obtain the molecular orbitals (MOs) and/or one-electron density matrix, and the post-HF correlation calculation that does not appear in the HF and Kohn-Sham (KS) density functional theory (DFT) calculations. This chapter reviews the linear-scaling quantum chemical calculation for the extension to open-shell and excited-state theories based on the divide-and-conquer (DC) method. Finally, it describes the efficiencies of the DC-UHF and UMP2 methods in measuring the central processing unit (CPU) time. The performance of the present DC-CIS, DC-TDDFT, and DC-SACCI methods is numerically assessed by comparing the results with those of conventional CIS, TDDFT, and SACCI calculations.

AB - The acceleration of ab initio electronic structure calculations has been one of the most important themes in the field of quantum chemistry since the mid-1980s when a series of single-reference theories starting from the Hartree-Fock (HF) method were already mature. The standard single-reference quantum chemical calculations consist of three time-consuming steps, namely, the Fock-matrix construction, its diagonalization to obtain the molecular orbitals (MOs) and/or one-electron density matrix, and the post-HF correlation calculation that does not appear in the HF and Kohn-Sham (KS) density functional theory (DFT) calculations. This chapter reviews the linear-scaling quantum chemical calculation for the extension to open-shell and excited-state theories based on the divide-and-conquer (DC) method. Finally, it describes the efficiencies of the DC-UHF and UMP2 methods in measuring the central processing unit (CPU) time. The performance of the present DC-CIS, DC-TDDFT, and DC-SACCI methods is numerically assessed by comparing the results with those of conventional CIS, TDDFT, and SACCI calculations.

KW - DC-UHF method

KW - Density functional theory

KW - Excited-state theory

KW - Hartree-Fock method

KW - Linear-scaling divide-and-conquer quantum chemical method

KW - Molecular orbitals

KW - Open-shell systems

KW - Quantum chemistry

KW - UMP2 method

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U2 - 10.1002/9781119129271.ch10

DO - 10.1002/9781119129271.ch10

M3 - Chapter

AN - SCOPUS:85052958905

SN - 9781119129240

SP - 297

EP - 321

BT - Fragmentation

PB - wiley

ER -