TITLE

Comparison between molecular orbital and surface integral calculations of the exchange energy for the homonuclear dimer ions He+2, Li+2, and Be+2

AUTHOR(S)
Chang, T. C.; Tang, K. T.
PUB. DATE
December 1995
SOURCE
Journal of Chemical Physics;12/22/1995, Vol. 103 Issue 24, p10580
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The exchange energy, defined as half of the energy splitting of the gerade and ungerade states of a molecular ion, is investigated by molecular orbital calculations and by the surface integral method. Numerical results of He+2, Li+2, and Be+2 are obtained through restricted Hartree–Fock, unrestricted Hartree–Fock and localized Heitler–London type calculations. The results of the surface integral method are analytical expressions which depend only on the ionization energy. While the approaches are completely different, the results are generally in good agreement. Discrepancies are highlighted with the hope of promoting further interplay of these complementary methods. © 1995 American Institute of Physics.
ACCESSION #
7646584

 

Related Articles

  • Independent particle theory with electron correlation. Beste, Ariana; Bartlett, Rodney J. // Journal of Chemical Physics;5/8/2004, Vol. 120 Issue 18, p8395 

    We formulate an effective independent particle model where the effective Hamiltonian is composed of the Fock operator and a correlation potential. Within the model the kinetic energy and the exchange energy can be expressed exactly leaving the correlation energy functional as the remaining...

  • DFT study of the geometrical and electronic structure of substituted cumulenes in netral and cationic forms. Podkopaeva, O. Yu.; Chizhov, Yu. V. // Journal of Structural Chemistry;May2006, Vol. 47 Issue 3, p420 

    The geometrical and basic energy parameters of monosubstituted cumulenes and their singly and doubly charged cations were calculated by the Hartree-Fock and density functional (DFT) methods at a B3LYP level of theory using the 6-31G( d) basis set. The substituent was fluorine, cyan, amino group,...

  • Energies of Atoms and Ions Calculated by the Hartree–Fock Method. Malykhanov, Yu. B.; Gorshunov, M. V. // Journal of Applied Spectroscopy;Nov2013, Vol. 80 Issue 5, p631 

    Energies of atoms from hydrogen to calcium and all their ions up to the one-electron atom inclusively that were calculated in the algebraic approximation of the Hartree–Fock method were compared with the experimental values obtained from ionization potentials. It was established that the...

  • Linearity condition for orbital energies in density functional theory: Construction of orbital-specific hybrid functional. Imamura, Yutaka; Kobayashi, Rie; Nakai, Hiromi // Journal of Chemical Physics;3/28/2011, Vol. 134 Issue 12, p124113 

    This study proposes a novel approach to construct the orbital-specific (OS) hybrid exchange-correlation functional by imposing the linearity condition: ∂2E/∂fi2|0≤fi≤1=∂&eh;i/∂fi|0≤fi≤1=0, where E, [variant_greek_epsilon]i, and fi represent the...

  • Finite-element multiconfiguration Hartree–Fock calculations on the excitation energies and the ionization potential of oxygen. Sundholm, Dage; Olsen, Jeppe; Alexander, S. A. // Journal of Chemical Physics;4/1/1992, Vol. 96 Issue 7, p5229 

    The 3P, 1D, and 1S states of oxygen and the 4S ground state of the oxygen cation have been studied using large numerical multiconfiguration Hartree–Fock calculations with systematically increased active spaces. The nonrelativistic valence limits for the excitation energies are 1.968 and...

  • Application of an efficient multireference approach to free-base porphin and metalloporphyrins: Ground, excited, and positive ion states. Chaudhuri, Rajat K; Freed, Karl F.; Chattopadhyay, Sudip; Mahapatra, Uttam Sinha // Journal of Chemical Physics;8/28/2011, Vol. 135 Issue 8, p084118 

    The improved virtual orbital-complete active space configuration interaction (IVO-CASCI) method is applied to determine the geometries of the ground state of free-base porphin and its metal derivatives, magnesium and zinc porphyrins. The vertical excitation energies and ionization potentials are...

  • Localized orbital/local origin method for calculation and analysis of NMR shieldings. Applications to 13C shielding tensors. Hansen, Aage E.; Bouman, Thomas D. // Journal of Chemical Physics;6/1/1985, Vol. 82 Issue 11, p5035 

    A theory of NMR shielding tensors is derived from Ramsey’s expressions, using the framework of the random phase approximation (RPA) and localized molecular orbitals. By expanding angular momentum terms relative to a local origin for each orbital and using properties of the RPA solutions,...

  • A partially restricted Hartree–Fock approach. Kollmar, Christian // Journal of Chemical Physics;3/1/1994, Vol. 100 Issue 5, p3683 

    We present a Hartree–Fock method which gives the molecular orbitals (MOs) of a single determinant wave function consisting of a restricted part (one orbital assigned to each pair of spin-up and spin-down electrons) and an unrestricted part (different orbitals for different spins). The MOs...

  • Theoretical study of GaAs surface passivation with Se. Gayen, Sanjukta; Ermler, Walter C.; Sandroff, Claude J. // Journal of Chemical Physics;1/1/1991, Vol. 94 Issue 1, p729 

    The mechanism for the quenching of surface states of GaAs by adsorbed elemental Se is studied using atomic clusters in ab initio Hartree–Fock calculations. Both the Ga- and the As-terminated surfaces are tied off with Se atoms in a 2×1 reconstruction. The most stable structure is...

Share

Read the Article

Courtesy of NEW JERSEY STATE LIBRARY

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics