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Core electron chemical shifts of hydrogen-bonded structures
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
School of Science and Technology, Örebro University.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-9123-8174
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-1763-9383
2009 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 468, no 4-6, 294-298 p.Article in journal (Refereed) Published
Abstract [en]

We examine the possibility to study hydrogen-bonded structures through core ionization energies. We use a recently derived self-interaction corrected density functional theory method where the core ionization energies for all chemically shifted elements are obtained by a single calculation of the ground state of the structures. A direct dependency between the hydrogen atom to acceptor atom bond length and the chemical shift of the core ionization energy of the acceptor atom is found, something that has rami. cations for the possibility of effective predictions of hydrogen bond lengths in hydrogen-bonded systems. This observation is verified by the conventional, much more time-consuming, self-consistent field calculations based on density functional theory.

Place, publisher, year, edition, pages
2009. Vol. 468, no 4-6, 294-298 p.
Keyword [en]
self-interaction correction, scalar couplings, level shift, solid-state, systems, acid
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-18101DOI: 10.1016/j.cplett.2008.12.023ISI: 000262412100040Scopus ID: 2-s2.0-58149400893OAI: oai:DiVA.org:kth-18101DiVA: diva2:336147
Note
QC 20100525. Tidigare titel: Core electron chemical shifts of hydrogen bonded networks using self interaction corrected DFTAvailable from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically 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

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Vahtras, OlavÅgren, Hans

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