Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0003-2729-0290
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0002-9123-8174
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0002-1763-9383
Show others and affiliations
2007 (English)In: Physical Review A. Atomic, Molecular, and Optical Physics, ISSN 1050-2947, E-ISSN 1094-1622, Vol. 76, no 2, 022506- p.Article in journal (Refereed) Published
Description
Abstract [en]

We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman , J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtained based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.

Place, publisher, year, edition, pages
2007. Vol. 76, no 2, 022506- p.
Keyword [en]
Benchmarking, Carbon, Density functional theory, Excited states, Ground state, Nitrogen, Optimization, Oxygen, Polarization, Energy shift, Organic molecules, Polarization propagator, Self-interaction energy
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-8410DOI: 10.1103/PhysRevA.76.022506ISI: 000249154900062Scopus ID: 2-s2.0-34548203136OAI: oai:DiVA.org:kth-8410DiVA: diva2:13722
Note
QC 20100914Available from: 2008-05-09 Created: 2008-05-09 Last updated: 2016-12-21Bibliographically approved
In thesis
1. Studies of Self-interaction Corrections in Density Functional Theory
Open this publication in new window or tab >>Studies of Self-interaction Corrections in Density Functional Theory
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The self-interaction error (SIE) in density functional theory (DFT) appears from the fact that the residual self-interaction in the Coulomb part and that in the exchange part do not cancel each other exactly. This error is responsible for the unphysical orbital energies of DFT and the failure to reproduce the potential energy curves of several physical processes.

The present thesis addresses several methods to solve the problem of SIE in DFT. A new algorithm is presented which is based on the Perdew-Zunger (PZ) energy correction and which includes the self-interaction correction (SIC) self-consistently (SC SIC PZ).

When applied to the study of hydrogen abstraction reactions, for which conventional DFT can not describe the processes properly, SC PZ SIC DFT produces reasonable potential energy curves along the reaction coordinate and reasonable transition barriers.

A semi-empirical SIC method is designed to correct the orbital energies. It is found that a potential coupling term is generally nonzero for all available approximate functionals. This coupling term also contributes to the self-interaction error. In this scheme, the potential coupling term is multiplied by an empirical parameter , introduced to indicate the strength of the potential coupling, and used to correct the PZ SIC DFT. Through a fitting scheme, we find that a unique can be used for C, N, O core orbitals in different molecules. Therefore this method is now used to correct the core orbital energies and relevant properties. This method is both efficient and accurate in predicting core ionization energies.

A new approach has been designed to solve the problem of SIE. A functional is constructed based on electron-electron interactions, Coulomb and exchange-correlation parts, which are free of SIE. A post-SCF procedure for this method has been implemented. The orbital energies thus obtained are of higher quality than in conventional DFT. For a molecular system, the orbital energy of the highest occupied molecular orbital (HOMO) is comparable to the experimental first ionization potential energy.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 51 p.
Series
Trita-BIO-Report, ISSN 1654-2312 ; 2008:11
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-4740 (URN)978-91-7178-964-8 (ISBN)
Public defence
2008-05-28, FB52, AlbaNova, Roslagstullsbacken, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100915Available from: 2008-05-09 Created: 2008-05-09 Last updated: 2010-09-15Bibliographically approved
2. Studies of self-interaction corrections in density functional theory
Open this publication in new window or tab >>Studies of self-interaction corrections in density functional theory
2007 (English)Licentiate thesis, comprehensive summary (Other scientific)
Place, publisher, year, edition, pages
Stockholm: KTH, 2007. v, 27 p.
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-4450 (URN)978-91-7178-648-7 (ISBN)
Presentation
2007-05-24, FD41, KTH, AlbaNova, Stockholm, 11:00
Opponent
Supervisors
Note
QC 20101119Available from: 2007-06-20 Created: 2007-06-20 Last updated: 2011-09-02Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Authority records BETA

Vahtras, OlavÅgren, Hans

Search in DiVA

By author/editor
Tu, GuangdeRinkevicius, ZilvinasVahtras, OlavÅgren, HansNorman, Patrick
By organisation
Theoretical Chemistry (closed 20110512)
In the same journal
Physical Review A. Atomic, Molecular, and Optical Physics
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 56 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf