+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Describing static correlation in bond dissociation by Kohn-Sham density functional theory

Describing static correlation in bond dissociation by Kohn-Sham density functional theory

Journal of Chemical Physics 122(9): 094116

We show that density functional theory within the RPA (random phase approximation for the exchange-correlation energy) provides a correct description of bond dissociation in H(2) in a spin-restricted Kohn-Sham formalism, i.e., without artificial symmetry breaking. We present accurate adiabatic connection curves both at equilibrium and beyond the Coulson-Fisher point. The strong curvature at large bond length implies important static (left-right) correlation, justifying modern hybrid functional constructions but also demonstrating their limitations. Although exact at infinite separation and accurate near the equilibrium bond length, the RPA dissociation curve displays unphysical repulsion at larger but finite bond lengths. Going beyond the RPA by including the exact exchange kernel (RPA+X), we find a similar repulsion. We argue that this deficiency is due to the absence of double excitations in adiabatic linear response theory. Further analyzing the H(2) dissociation limit we show that the RPA+X is not size consistent, in contrast to the RPA.

Please choose payment method:

(PDF emailed within 0-6 h: $19.90)

Accession: 048739104

Download citation: RISBibTeXText

PMID: 15836121

DOI: 10.1063/1.1858371

Related references

Dynamical correction to linear Kohn-Sham conductances from static density functional theory. Physical Review Letters 111(3): 030601, 2013

Strong correlation in Kohn-Sham density functional theory. Physical Review Letters 109(24): 246402, 2012

Quantum-mechanical interpretation of the exchange-correlation potential of Kohn-Sham density-functional theory. Physical Review Letters 62(5): 489-492, 1989

MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids. Journal of Chemical Theory and Computation 12(3): 1280-1293, 2016

Hybrid ab initio Kohn-Sham density functional theory/frozen-density orbital-free density functional theory simulation method suitable for biological systems. Journal of Chemical Physics 128(1): 014101, 2008

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer. Journal of Chemical Theory and Computation 11(8): 3643-3649, 2015

Increasing the applicability of density functional theory. III. Do consistent Kohn-Sham density functional methods exist?. Journal of Chemical Physics 137(13): 134102, 2012

An average-of-configuration method for using Kohn-Sham density functional theory in modeling ligand-field theory. Inorganic Chemistry 42(13): 4088-4097, 2003

Assessment of Kohn-Sham density functional theory and Møller-Plesset perturbation theory for ionic liquids. Physical Chemistry Chemical Physics 15(32): 13664-13675, 2013

Self-averaging stochastic Kohn-Sham density-functional theory. Physical Review Letters 111(10): 106402, 2013

Open-system Kohn-Sham density functional theory. Journal of Chemical Physics 136(9): 094105, 2012

Exchange energy in Kohn-Sham density-functional theory. Physical Review. A Atomic Molecular and Optical Physics 51(5): 3571-3575, 1995

The calculation of the static first and second susceptibilities of crystalline urea: A comparison of Hartree-Fock and density functional theory results obtained with the periodic coupled perturbed Hartree-Fock/Kohn-Sham scheme. Journal of Chemical Physics 131(21): 214704, 2009

Perspective: Kohn-Sham density functional theory descending a staircase. Journal of Chemical Physics 145(13): 130901, 2016

Local Fitting of the Kohn-Sham Density in a Gaussian and Plane Waves Scheme for Large-Scale Density Functional Theory Simulations. Journal of Chemical Theory and Computation 13(5): 2202-2214, 2017