Self-consistent field method for open-shell systems within the density-matrix functional theory

被引：4

作者：

Irimia, Marinela ^{[1
]}

Wang, Jian ^{[2
]}

机构：

[1] Huzhou Univ, Int Sch, Huzhou, Zhejiang, Peoples R China

[2] Huzhou Univ, Sch Sci, Huzhou 313000, Zhejiang, Peoples R China

来源：

JOURNAL OF COMPUTATIONAL CHEMISTRY | 2024年 / 45卷 / 04期

基金：

美国国家科学基金会;

关键词：

density matrix functional theory; electron correlation; information entropy; UHF; EXCHANGE-CORRELATION-ENERGY; PHASE DILEMMA; ORBITALS; CONVERGENCE; CUMULANT; ENTROPY; HARTREE; STATES;

D O I：

10.1002/jcc.27232

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The unrestricted Hartree-Fock method is extended to correlation calculation within the density-matrix functional theory. The method is derived from an entropic cumulant functional for the correlation energy. The eigenvalue equations for the spin-orbitals are modified by the orbital occupation numbers. The Euler equation for the occupation numbers results in the Fermi-Dirac distribution, which is very efficient to update as soon as the orbital eigenvalue equations are solved. The method is demonstrated on the ground state of O2$$ {}_2 $$.

引用

页码：222 / 229

页数：8

共 50 条

[21] On the origins of spontaneous spherical symmetry-breaking in open-shell atoms through polymer self-consistent field theory
LeMaitre, Phil A.
Thompson, Russell B.
JOURNAL OF CHEMICAL PHYSICS, 2023, 158 (06):
[22] THE DENSITY MATRIX IN SELF-CONSISTENT FIELD THEORY .1. ITERATIVE CONSTRUCTION OF THE DENSITY MATRIX
MCWEENY, R
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1956, 235 (1203) : 496 - 509
[23] RELATIVISTIC SELF-CONSISTENT-FIELD THEORY FOR OPEN-SHELL ATOMS .1.
LECLERCQ, JM
PHYSICAL REVIEW A, 1970, 1 (05): : 1358 - &
[24] Alternative Technique for the Constrained Variational Problem Based on an Asymptotic Projection Method: II. Applications to Open-Shell Self-Consistent Field Theory
Glushkov, Vitaly N.
Gidopoulos, Nikitas I.
Wilson, Stephen
FRONTIERS IN QUANTUM SYSTEMS IN CHEMISTRY AND PHYSICS, 2008, 18 : 451 - +
[25] OPEN-SHELL RESTRICTED HARTREE-FOCK DENSITY-MATRIX DIRECT CALCULATIONS
MESTECHKIN, MM
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1980, 18 (01) : 19 - 23
[26] BOND INDEX OF 2 OPEN-SHELL MOLECULES USING A ZDO DENSITY-MATRIX
RITSCHL, F
ZEITSCHRIFT FUR CHEMIE, 1984, 24 (06): : 234 - 235
[27] Density functional theory for open-shell singlet biradicals
Grafenstein, J
Kraka, E
Cremer, D
CHEMICAL PHYSICS LETTERS, 1998, 288 (5-6) : 593 - 602
[28] NUMERICAL-METHOD FOR THE OPEN-SHELL RESTRICTED HARTREE-FOCK DENSITY-MATRIX DIRECT CALCULATION
MESTECHKIN, MM
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1985, 27 (06) : 653 - 664
[29] Self-consistent atomic deformation method for application of density functional theory
Boyer, L. L.
Stokes, H. T.
Ossowski, M. M.
Mehl, M. J.
PHYSICAL REVIEW B, 2008, 78 (04)
[30] THE DENSITY MATRIX IN SELF-CONSISTENT FIELD THEORY .2. APPLICATIONS IN THE MOLECULAR ORBITAL THEORY OF CONJUGATED SYSTEMS
MCWEENY, R
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1956, 237 (1210): : 355 - 371

← 1 2 3 4 5 →