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Localized orbital corrections applied to thermochemical errors in density functional theory: The role of basis set and application to molecular reactions
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10.1063/1.3008062
/content/aip/journal/jcp/129/21/10.1063/1.3008062
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/21/10.1063/1.3008062

Figures

Image of FIG. 1.
FIG. 1.

The histogram of errors of across the G3 data set in the aug-cc-pVTZ basis: the white and black bars represent the pure and the LOC-corrected functionals, respectively.

Image of FIG. 2.
FIG. 2.

The histogram of errors of across the G3 data set in the basis: the white and black bars represent the pure and the LOC-corrected functionals, respectively.

Tables

Generic image for table
Table III.

The 22 parameters fit to both the extended G2 and G3 data sets for each basis set using the classic B3LYP hybrid functional.

Generic image for table
Table I.

The MUEs of enthalpies of formation at 298.15 K of Pople’s extended G2 and full G3 set in kcal/mol. Pure values are the MUEs without any LOCs. denotes the use of LOCs fit to the extended G2 data set. denotes the use of LOCs fit to the entire G3 data set.

Generic image for table
Table II.

The MUEs of enthalpies of formation at 298.15 K of Pople’s complement of G2 with respect to G3 (75 compounds in total) in kcal/mol. The error is defined as the experimental value minus the DFT value. Pure values are the MUEs without any LOCs. denotes the use of LOCs fit to the extended G2 data set. denotes the use of LOCs fit to the entire G3 data set.

Generic image for table
Table IV.

The 22 parameters fit to both the extended G2 and G3 data sets for each basis set using the classic M05-2X hybrid functional.

Generic image for table
Table V.

The MRG2-TRN set and the errors of the constituent reactions obtained with B3LYP and M05-2X in the basis set. The errors are given in kcal/mol. The error is defined as the experimental value minus the DFT value. All errors are with respect to the reaction enthalpies obtained from the experimental enthalpies of formation of the individual compounds. The coefficients used in the LOC scheme were obtained from the solution of the linear system constructed after the MRG2-TRN set.

Generic image for table
Table VI.

The performance of different parametrizations of the LOC approach on various sets of atomization and molecular reactions with compounds from G2 set only. The errors are given in kcal/mol. The coefficients of the LOC parametrization were first found by solving a system of linear equations in the least-square sense. Then these coefficients were used in the application of the LOC scheme to a set of reactions. The first row of the table indicates the equations from which the coefficients were derived, whereas the second row shows the reactions to which the coefficients were applied. A stands for the atomization reactions of the G2 set (147 reactions), TRN stands for the MRG2 training set (90 reactions), and TST stands for the MRG2 test set (60 reactions). The MUEs of the enthalpies of formation for the LOC scheme are compared to the analogous values of the pure (without LOC) DFT method.

Generic image for table
Table VII.

The performance of the M06-2X functional and its LOC analog on the G2 set. The errors are given in kcal/mol.

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/content/aip/journal/jcp/129/21/10.1063/1.3008062
2008-12-02
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Localized orbital corrections applied to thermochemical errors in density functional theory: The role of basis set and application to molecular reactions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/21/10.1063/1.3008062
10.1063/1.3008062
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