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Basis set dependence of the doubly hybrid XYG3 functional
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0003-0007-0394
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University.
2010 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 133, no 10, 104105- p.Article in journal (Refereed) Published
Abstract [en]

In the present study, we investigated the basis set dependence of XYG3, a newly developed doubly hybrid functional [Y. Zhang, X. Xu, and W. A. Goddard III, Proc. Natl. Acad. Sci. U.S.A. 106, 4963 (2009)], in prediction of (1) heats of formation (HOFs), (2) bond dissociation enthalpies (BDEs), (3) reaction barrier heights (RBHs), and (4) nonbonded interactions (NBIs). We used basis sets of triple-zeta quality starting from 6-311+G(d,p) with increasing completeness of the polarization functions to the largest Pople-type basis set 6-311++G(3df,3pd) and found that there was a continued improvement with larger basis sets. We showed that while HOF predictions were prone to basis set deficiencies, the basis set dependences in calculating BDEs, RBHs, and NBIs were mild. All of them converged fast with the increase of basis set size. We extended XYG3 to propose the XYG3o functional which was specifically optimized for a particular basis set in order to enhance its performance when using basis set of moderate size. With the 6-311+G(2df,p) basis set, XYG3o led to MADs of 2.56 kcal/mol for HOFs of the G3/99 set, 1.17 kcal/mol for BDEs of the BDE92/07 set, 1.11 kcal/mol for RBHs of the NHTBH38/04 and HTBH38/04 sets, and 0.40 kcal/mol for NBIs of the NCIE31/05 set, being comparable to those obtained by using XYG3/6-311++G(3df,3pd).

Place, publisher, year, edition, pages
2010. Vol. 133, no 10, 104105- p.
Keyword [en]
Basis sets, Bond dissociation enthalpies, Heats of formation, Nonbonded interaction, Polarization functions, Reaction barrier heights, Triple-zeta quality
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-26635DOI: 10.1063/1.3488649ISI: 000282475400011ScopusID: 2-s2.0-77956938075OAI: diva2:374576
QC 20101206Available from: 2010-12-06 Created: 2010-11-26 Last updated: 2011-06-07Bibliographically approved
In thesis
1. A new generation density functional towards chemical accuracy
Open this publication in new window or tab >>A new generation density functional towards chemical accuracy
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Density functional theory (DFT) has become the leading method in calculating theelectronic structures and properties from first principles. In practical applicationsof DFT in the frame work of Kohn-Sham (KS) method, an approximate exchange-correlation functional has to be chosen. Hence, the success of a DFT calculationcritically depends on the quality of the exchange-correlation functional.This thesis focuses on the development and validation of the so-called dou-bly hybrid density functionals (DHDFs). DHDFs present a new generation offunctionals, which not only have a non-local orbital-dependent component in theexchange part, but also incorporate the information of unoccupied orbitals in thecorrelation part. I will first give an overview of modern DFT in the introductorychapters, emphasizing the theoretical bases of a newly developed DHDF, XYG3.I will then present further examination of XYG3 and new development on top ofXYG3, leading to XYG3o and XYG3s. Attempts have also been made to extractband structure information of a periodic system from cluster model calculations.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. 56 p.
Trita-BIO-Report, ISSN 1654-2312
National Category
Industrial Biotechnology
urn:nbn:se:kth:diva-33857 (URN)978-91-7501-022-9 (ISBN)
Public defence
2011-06-15, FB42, AlbaNova, Stockholm, 10:00 (English)
QC 20110607Available from: 2011-06-07 Created: 2011-05-20 Last updated: 2011-06-07Bibliographically approved

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