Two-electron distribution functions and short-range electron correlations of atoms and molecules by first principles T-matrix calculations

Noguchi, Yoshifumi; Ishii, Soh; Ohno, Kaoru
September 2006
Journal of Chemical Physics;9/21/2006, Vol. 125 Issue 11, p114108
Academic Journal
The accurate first principles description of the correlations between electrons has been a topic of interest in molecular physics. We have reported in our previous paper [J. Chem. Phys. 123, 144112 (2005)] that the T matrix, which is the ladder diagrams up to the infinite order, can accurately represent the short-range electron correlations while calculating the double ionization energy spectra of atoms and molecules. In this paper, we calculate the two-electron distribution functions of real systems (Ar, CO, CO2, and C2H2) from the eigenvalue equation associated with the Bethe-Salpeter equation for the T matrix by beginning with the local density approximation of the density functional theory and the GW approximation. We found that when the interelectron distance is very small, the Coulomb hole appears between antiparallel spin electrons due to the short-range repulsive Coulomb interaction. The resulting two-electron distribution functions clearly show the Coulomb hole.


Related Articles

  • Long-range corrected hybrid functionals for Ï€-conjugated systems: Dependence of the range-separation parameter on conjugation length. Körzdörfer, Thomas; Sears, John S.; Sutton, Christopher; Brédas, Jean-Luc // Journal of Chemical Physics;Nov2011, Vol. 135 Issue 20, p204107 

    Long-range corrected (range-separated hybrid) functionals represent a relatively new class of functionals for generalized Kohn-Sham theory that have proven to be very successful, for instance, when it comes to predicting ionization potentials and energy gaps for a wide range of molecules and...

  • Energy bounds for the spinless Salpeter equation. Hall, Richard L.; Lucha, Wolfgang; Scho¨berl, Franz F. // Journal of Mathematical Physics;Nov2001, Vol. 42 Issue 11, p5228 

    Reports on the spectrum of Salpeter Hamiltonian equations with a central potential in three spatial dimensions. Eigenvalue equation of the operator; Emergence of an equation of motion as a well-defined standard approximation to the Bethe-Salpeter formalism for the description of bound states...

  • Molecular grand-canonical ensemble density functional theory and exploration of chemical space. von Lilienfeld, O. Anatole; Tuckerman, Mark E. // Journal of Chemical Physics;10/21/2006, Vol. 125 Issue 15, p154104 

    We present a rigorous description of chemical space within a molecular grand-canonical ensemble multi-component density functional theory framework. A total energy density functional for chemical compounds in contact with an electron and a proton bath is introduced using Lagrange multipliers...

  • Density functional study of double ionization energies. Chong, D. P. // Journal of Chemical Physics;2/28/2008, Vol. 128 Issue 8, p084112 

    In this paper, double ionization energies (DIEs) of gas-phase atoms and molecules are calculated by energy difference method with density functional theory. To determine the best functional for double ionization energies, we first study 24 main group atoms in the second, third, and fourth...

  • Carbonyl sulphide under strong laser field: Time-dependent density functional theory. Bilalbegović, G. // European Physical Journal D -- Atoms, Molecules, Clusters & Opti;Jan2009, Vol. 49 Issue 1, p43 

    The first 52 fs of a time evolution of the electron density in OCS after an interaction with an intense sub 10 fs laser pulse are studied using the time-dependent density functional theory. The nuclear motion in this linear trimer is simulated by the classical molecular dynamics method. Laser...

  • Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials. Verma, Prakash; Bartlett, Rodney J. // Journal of Chemical Physics;5/14/2014, Vol. 140 Issue 18, p18A534-1 

    This paper's objective is to create a "consistent" mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization...

  • Quasiparticle energies, excitonic effects and optical absorption spectra of small-diameter single-walled carbon nanotubes. Spataru, C. D.; Ismail-Beigi, S.; Benedict, L. X.; Louie, S. G. // Applied Physics A: Materials Science & Processing;2004, Vol. 78 Issue 8, p1129 

    We present a first-principles study of the effects of many-electron interactions on the optical properties of single-walled carbon nanotubes. Motivated by recent experiments, we have carried out ab initio calculations on the single-walled carbon nanotubes (3, 3), (5, 0) and (8, 0). The...

  • Double excitations in correlated systems: A many-body approach. Sangalli, Davide; Romaniello, Pina; Onida, Giovanni; Marini, Andrea // Journal of Chemical Physics;1/21/2011, Vol. 134 Issue 3, p034115 

    A coherent approach to the description of double excitations in correlated materials is presented: We derive stringent mathematical conditions on the algebraical structure of the Bethe-Salpeter and time-dependent density functional theory kernels that avoid the occurrence of spurious and...

  • Optical absorption spectra of finite systems from a conserving Bethe-Salpeter equation approach. Pal, G.; Pavlyukh, Y.; Hübner, W.; Schneider, H. C. // European Physical Journal B -- Condensed Matter;Feb2011, Vol. 79 Issue 3, p327 

    We present a method for computing optical absorption spectra by means of a Bethe-Salpeter equation approach, which is based on a conserving linear response calculation for electron-hole coherences in the presence of an external electromagnetic field. This procedure allows, in principle, for the...


Read the Article


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

Try another library?
Sign out of this library

Other Topics