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A new generation density functional towards chemical accuracy
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
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.
Series
Trita-BIO-Report, ISSN 1654-2312
National Category
Industrial Biotechnology
Identifiers
URN: urn:nbn:se:kth:diva-33857ISBN: 978-91-7501-022-9OAI: oai:DiVA.org:kth-33857DiVA: diva2:418183
Public defence
2011-06-15, FB42, AlbaNova, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20110607Available from: 2011-06-07 Created: 2011-05-20 Last updated: 2011-06-07Bibliographically approved
List of papers
1. Accurate Bond Dissociation Enthalpies by Using Doubly Hybrid XYG3 Functional
Open this publication in new window or tab >>Accurate Bond Dissociation Enthalpies by Using Doubly Hybrid XYG3 Functional
2011 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 32, no 9, 1824-1838 p.Article in journal (Refereed) Published
Abstract [en]

In this work, we examine the performance of XYG3, a newly developed doubly hybrid density functional (Zhang, Xu, and Goddard III, Proc Natl Acad Sci USA 2009, 106, 4963), to calculate covalent bond dissociation enthalpy (BDE). We use 5 atoms, 32 molecular radicals, and 116 closed-shell molecules to set up 142 bond dissociation reactions. For the total of 148 heats of formation (HOFs) and 142 BDEs, XYG3 leads to mean absolute deviations (MADs) of 1.45 and 1.87 kcal/mol, respectively. In comparison with some other functionals, MADs for HOFs are 2.31 (M06-2X), 2.98 (B2PLYP-D), 3.04 (BMK), 3.96 (B3LYP), 4.47 (B2PLYP), 5.42 (B2GP-PLYP), 6.46 (PBE0), and 29.93 kcal/mol (B3P86), and the corresponding errors for BDEs are 2.06 (M06-2X), 2.25 (BMK), 2.51 (B2PLYP-D), 2.89 (B2GP-PLYP), 3.30 (B3P86), 3.44 (B2PLYP), 3.87 (PBE0), and 6.14 kcal/mol (B3LYP). (C) 2011 Wiley Periodicals, Inc. J Comput Chem 32: 1824-1838, 2011

Keyword
DFT, XYG3, B3LYP, bond dissociation enthalpy
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-34215 (URN)10.1002/jcc.21764 (DOI)000290531000005 ()2-s2.0-79955471670 (ScopusID)
Note
QC 20110607Available from: 2011-06-07 Created: 2011-05-30 Last updated: 2011-06-07Bibliographically approved
2. Trends in R-X Bond Dissociation Energies (R-center dot = Me, Et, i-Pr, t-Bu, X-center dot = H, Me, Cl, OH)
Open this publication in new window or tab >>Trends in R-X Bond Dissociation Energies (R-center dot = Me, Et, i-Pr, t-Bu, X-center dot = H, Me, Cl, OH)
2010 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 6, no 5, 1462-1469 p.Article in journal (Refereed) Published
Abstract [en]

Trends for R X bond dissociation energies have been examined with density functional methods of B3LYP, BMK, M06-2X, MC3MPW, B2PLYP, MCG3-MPW, and XYG3, as well as 03, MCG3/3, G3X, and 04 theories as functions of alkylation (i.e., IT = Me, Et, i-Pr, (-Bu) and X' substitution (i.e., X' = H, Me, Cl, OH). The results highlight the physical origin of success or failure of each method and demonstrate the good agreement with experimental results for G4, MCG3-MPW, and XYG3. The last holds great promise as a reliable method that is applicable to larger systems.

National Category
Physical Chemistry Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:kth:diva-27907 (URN)10.1021/ct100010d (DOI)000277408500003 ()2-s2.0-77952362326 (ScopusID)
Note
QC 20110104Available from: 2011-01-04 Created: 2011-01-03 Last updated: 2012-03-22Bibliographically approved
3. Basis set dependence of the doubly hybrid XYG3 functional
Open this publication in new window or tab >>Basis set dependence of the doubly hybrid XYG3 functional
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).

Keyword
Basis sets, Bond dissociation enthalpies, Heats of formation, Nonbonded interaction, Polarization functions, Reaction barrier heights, Triple-zeta quality
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-26635 (URN)10.1063/1.3488649 (DOI)000282475400011 ()2-s2.0-77956938075 (ScopusID)
Note
QC 20101206Available from: 2010-12-06 Created: 2010-11-26 Last updated: 2011-06-07Bibliographically approved
4. XYG3s: Speedup of the XYG3 fifth-rung density functional with scaling-all-correlation method
Open this publication in new window or tab >>XYG3s: Speedup of the XYG3 fifth-rung density functional with scaling-all-correlation method
2010 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 132, no 19, 194105- p.Article in journal (Refereed) Published
Abstract [en]

Recently, we proposed a new version of doubly hybrid functional, XYG3 [Y. Zhang, X. Xu, and W. A. Goddard III, Proc. Natl. Acad. Sci. U.S.A. 106, 4963 (2009)], which not only has a nonlocal orbital-dependent component in the exchange term (Hartree-Fock-like exchange), but also contains information about the unoccupied Kohn-Sham orbitals in the correlation part (PT2 double excitation). In the present work, we examine the frozen-core approximation and Truhlar's scaling-all-correlation (SAC) method in order to accelerate the PT2 evaluations. We adopt the SAC idea and extend XYG3 to propose XYG3s that uses a uniform scaling parameter for the PT2 correlation. We conclude that XYG3s is both fast and accurate for thermochemistry, bond dissociation enthalpies, reaction barrier heights, and nonbonded interactions of main group molecules. In addition, the accuracy remains nearly constant with system size.

Keyword
Bond dissociation enthalpies, Density functionals, Double excitations, Frozen-core approximations, Hartree-fock, Kohn-Sham orbitals, Main group, Nonbonded interaction, Nonlocal, Reaction barrier heights, Scaling parameter, System size, Thermochemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-27578 (URN)10.1063/1.3424845 (DOI)000277970100006 ()2-s2.0-77952983044 (ScopusID)
Note
QC 20101214Available from: 2010-12-14 Created: 2010-12-13 Last updated: 2011-06-07Bibliographically approved
5. The RRS-PBC Method: Bridge Finite Cluster to Crystalline Bulk Solid
Open this publication in new window or tab >>The RRS-PBC Method: Bridge Finite Cluster to Crystalline Bulk Solid
Show others...
(English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448Article in journal (Other academic) Submitted
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-34419 (URN)
Note
QS 20120328Available from: 2011-06-07 Created: 2011-06-07 Last updated: 2012-03-28Bibliographically approved

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