1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems
Rent:
Rent this article for
USD
10.1063/1.3700154
/content/aip/journal/jcp/136/15/10.1063/1.3700154
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/15/10.1063/1.3700154

Figures

Image of FIG. 1.
FIG. 1.

Computed Boys and Bernadi CP correction for the S66×8 benchmark set with HF, B3LYP, and BLYP with the basis sets (a) MINIS and (b) 6-31G*. The set consists of 66 systems (abscissa) with eight varying distances. The CP correction for each distance (ordinate) results in 528 data points.

Image of FIG. 2.
FIG. 2.

Deviations between the Boys and Bernadi CP correction (ΔBB-CP) and the gCP correction (ΔgCP) for the S66×8 dimers in kcal/mol for B3LYP/6-31G* and HF/MINIS. The set consists of 66 systems (abscissa) with eight varying distances. The deviation (ΔgCP − ΔBB-CP) for each distance (ordinate) results in 528 data points. Positive values indicate an overestimation.

Image of FIG. 3.
FIG. 3.

Potential energy curve of of a peptide-ethene complex (taken from the S66 set, depicted in the top right corner). The dimers are displaced along the vectors connecting their center-of-mass points by the multipliers 0.8, 0.9, 0.95, 1.00, 1.05, 1.10, 1.25, 1.50, 1.75, 2.00. The dispersion energy E disp from SAPT and DFT-D3 is plotted along with the Boys and Bernadi counterpoise (BB-CP) and gCP correction.

Image of FIG. 4.
FIG. 4.

View of the folded (top) and extended (bottom) PM6-DH+ optimized (gas-phase) conformers of crambin.

Image of FIG. 5.
FIG. 5.

Relaxed rotational energy profile of the FGF tripeptide in kcal/mol. The dihedral angle δ between the atoms indicated in black is varied in steps of 20° and held fixed in subsequent optimizations.

Image of FIG. 6.
FIG. 6.

B97-D3 and HF-D3 interaction energies for 24 protein-ligand complexes with and without gCP correction. The LPNO-CEPA/1 and B97-D3/def2-TZVP reference values are taken from Ref. 132.

Image of FIG. 7.
FIG. 7.

Comparison of BB-CP- and gCP-optimized structures with uncorrected ones for the S22 benchmark set. Deviation from the center-of-mass distances of the MP2 reference structures is plotted in Å. (a) HF-D3/SV, (b) B3LYP-D3/6-31G*, and (c) HF-D3/MINIS.

Image of FIG. 8.
FIG. 8.

HF-D3/def2-QZVP optimized structure of 9-helicene. Two intramolecular distances of raw and gCP-corrected HF-D3/SV structures are compared with the shown reference structure.

Image of FIG. 9.
FIG. 9.

TPSS-D3/def2-QZVP structure of the (RhCl(PH3))2 dimer.

Tables

Generic image for table
Table I.

Parameters for the gCP correction and fit quality (RMS deviation in kcal/mol) of the fit against Boys and Bernadi CP values for the S66×8 dimer geometries. The arithmetic mean of the BB-CP correction is also given (in kcal/mol).

Generic image for table
Table II.

Mean absolute deviations (MADs) for S66 benchmark set in kcal/mol. The column “+ gCP” indicates that the gCP correction is added to the DFT-D3 results. The methods are ordered according to increasing basis set quality.

Generic image for table
Table III.

Mean absolute deviations (MADs) for DFT-NL for the S66 benchmark set in kcal/mol. The column “+ gCP” indicates that the gCP correction is added to the DFT-NL results. The DFT-NL calculations have been performed non-self-consistently, except those indicated by (SC).

Generic image for table
Table IV.

Mean absolute deviations (MADs) for S22 benchmark set in kcal/mol. The column “+ gCP” indicates that the gCP correction is added to the DFT-D3 or DFT-NL results. The DFT-NL calculations have been performed non-self-consistently.

Generic image for table
Table V.

Energy decomposition analysis of the interaction energy of the benzene-water complex (system 54) of the S66 benchmark set in kcal/mol. The “def2” label is omitted for clarity. The individual terms are electrostatic interaction ES, Pauli, or exchange repulsion EX, induction energy IND, charge-transfer energy CT, and the high-order-coupling term MIX. The gCP correction and the Boys and Bernadi counterpoise correction BB-CP are given. The BB-CP-correction only affects the EX,CT and MIX terms.

Generic image for table
Table VI.

Selected systems from the WATER27 set as a test case for a cluster-type CP correction. ssf-CP and gCP values in kcal/mol are compared for the HF/MINIS and DFT(=B3LYP)/def2-SVP level of theory.

Generic image for table
Table VII.

Relative energies (kcal/mol) of two crambin conformers (extended and folded) calculated with BLYP-D3 and various basis sets. Structures are optimized at the PM6-DH+ level of theory.

Generic image for table
Table VIII.

Intramolecular BSSE calculated for the FGF-tripeptide in kcal/mol. Comparison with Jensen's ACP approach.

Loading

Article metrics loading...

/content/aip/journal/jcp/136/15/10.1063/1.3700154
2012-04-16
2014-04-23
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A geometrical correction for the inter- and intra-molecular basis set superposition error in Hartree-Fock and density functional theory calculations for large systems
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/15/10.1063/1.3700154
10.1063/1.3700154
SEARCH_EXPAND_ITEM