DIRECT DETERMINATION OF PURE-STATE DENSITY MATRICES .I. SOME SIMPLE INTRODUCTORY CALCULATIONS

被引:30
作者
CLINTON, WL
NAKHLEH, J
WUNDERLI.F
机构
[1] Department of Physics, Georgetown University, Washington, DC
[2] VARO, Incorporated, Garland, TX 75040
[3] Department of Physical Science, College of the Virgin Islands, St. Thomas
来源
PHYSICAL REVIEW | 1969年 / 177卷 / 01期
关键词
D O I
10.1103/PhysRev.177.1
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
A method is developed for the semiempirical determination of an electron density in small diatomic molecules. The method involves primarily the electrostatic and virial theorems and empirical potential curve data. The density has been determined, using Slater-type basis functions, for the molecules H2+, H2, He2, Li2, and N2. Expectation values are calculated and compared to exact or Hartree-Fock values. A theoretical discussion of the semiempirical densities via a natural-orbital analysis is given. These analyses show that (a) the electrostatic and virial theorems are effective when used to determine unknown parameters in a first-order density but that (b) some additional means must be provided to ensure N representability. © 1969 The American Physical Society.
引用
收藏
页码:1 / &
相关论文
共 14 条
[1]   THE USE OF THE HELLMANN-FEYNMAN THEOREM TO CALCULATE MOLECULAR ENERGIES [J].
BADER, RFW .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1960, 38 (11) :2117-2127
[2]   FORCES IN MOLECULES .1. APPLICATION OF THE VIRIAL THEOREM [J].
CLINTON, WL .
JOURNAL OF CHEMICAL PHYSICS, 1960, 33 (06) :1603-1606
[3]   STRUCTURE OF FERMION DENSITY MATRICES [J].
COLEMAN, AJ .
REVIEWS OF MODERN PHYSICS, 1963, 35 (03) :668-&
[4]   Forces in molecules [J].
Feynman, RP .
PHYSICAL REVIEW, 1939, 56 (04) :340-343
[5]   ELECTRONIC STRUCTURE OF SIMPLE HOMONUCLEAR DIATOMIC MOLECULES .2. LITHIUM MOLECULE [J].
ISHIGURO, E ;
KAYAMA, K ;
KOTANI, M ;
MIZUNO, Y .
JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN, 1957, 12 (12) :1355-1385
[6]   CHARGE DISTRIBUTION IN THE HYDROGEN MOLECULE [J].
KARPLUS, M .
JOURNAL OF CHEMICAL PHYSICS, 1956, 25 (03) :605-606
[7]   ANALYSIS OF CHARGE DISTRIBUTIONS - HYDROGEN FLUORIDE [J].
KERN, CW ;
KARPLUS, M .
JOURNAL OF CHEMICAL PHYSICS, 1964, 40 (05) :1374-+
[8]  
LOWDIN PO, 1959, ADV CHEM PHYS, V2, P207
[9]   SOME RECENT ADVANCES IN DENSITY MATRIX THEORY [J].
MCWEENY, R .
REVIEWS OF MODERN PHYSICS, 1960, 32 (02) :335-369
[10]   ELECTRONIC POPULATION ANALYSIS ON LCAO-MO MOLECULAR WAVE FUNCTIONS .1. [J].
MULLIKEN, RS .
JOURNAL OF CHEMICAL PHYSICS, 1955, 23 (10) :1833-1840