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Basis set converged weak interaction energies from conventional and explicitly correlated coupled-cluster approach
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10.1063/1.4800981
/content/aip/journal/jcp/138/15/10.1063/1.4800981
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/15/10.1063/1.4800981

Figures

Image of FIG. 1.
FIG. 1.

Performance of the CCSD(T) and CCSD(T)-F12b approaches for the radial potential energy curve of the He–CH4 complex passing through the global minimum. The values displayed are relative to the benchmark interaction energy (estimated from the scaled-triples CCSD(T)-F12c/aQZM calculation) and normalized by the absolute deviation of the CCSD(T)/aQZ interaction energy from the benchmark at a given intermolecular distance R.

Image of FIG. 2.
FIG. 2.

Performance of the CCSD(T) and CCSD(T)-F12b approaches for the radial potential energy curve of the CH4–CH4 complex passing through the global minimum. The values displayed are relative to the benchmark interaction energy (estimated from the scaled-triples CCSD(T)-F12c/aQZM calculation) and normalized by the absolute deviation of the CCSD(T)/aQZ interaction energy from the benchmark at a given intermolecular distance R.

Image of FIG. 3.
FIG. 3.

Performance of the CCSD(T) and CCSD(T)-F12b approaches for the radial potential energy curve of the H2O–H2O complex passing through the global minimum. The values displayed are relative to the benchmark interaction energy (estimated from the scaled-triples CCSD(T)-F12c/aQZM calculation) and normalized by the absolute deviation of the CCSD(T)/aQZ interaction energy from the benchmark at a given intermolecular distance R.

Image of FIG. 4.
FIG. 4.

Dependence of the MP2-F12 (left panels) and CCSD(T)-F12b (right panels) interaction energies on the geminal exponent β for the He–CH4 (top) and CH4–H2O (bottom) dimers. The MP2-F12 calculations use the 3C(FIX) Ansatz just like the CCSD(T)-F12b approach. The triples term in CCSD(T)-F12b is not scaled.

Tables

Generic image for table
Table I.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the He–H2O complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −34.34 ± 0.07 cm−1.

Generic image for table
Table II.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the Ar–H2O complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −139.52 ± 0.12 cm−1.

Generic image for table
Table III.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the He–CH4 complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −29.43 ± 0.08 cm−1.

Generic image for table
Table IV.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the Ar–CH4 complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −141.16 ± 0.41 cm−1.

Generic image for table
Table V.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the H2O–H2O complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −1745.0 ± 1.2 cm−1.

Generic image for table
Table VI.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the CH4–H2O complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −354.8 ± 0.5 cm−1.

Generic image for table
Table VII.

CCSD(T)/aXZ and CCSD(T)-F12b/aXZ interaction energies (in cm−1) for the minimum geometry of the CH4–CH4 complex as functions of the basis set cardinal number X. The extrapolated value (rows “ext.”) in the X column is computed using interaction energies in bases a(X − 1)Z and aXZ. The midbond functions are chosen as hydrogenic functions from the same aXZ orbital basis set. The benchmark CCSD(T)/CBS interaction energy amounts to −187.30 ± 0.30 cm−1.

Generic image for table
Table VIII.

Mean unsigned errors (MUE, in cm−1) of different CCSD(T)/CCSD(T)-F12 variants and basis sets. The errors are averaged over the van der Waals minimum geometries for the seven dimers considered in this work. The benchmark CCSD(T)/CBS interaction energies have been obtained as described in Sec. III .

Generic image for table
Table IX.

Mean unsigned relative errors (MURE, in percent) of different CCSD(T)/CCSD(T)-F12 variants and basis sets. The errors are averaged over the van der Waals minimum geometries for the seven dimers considered in this work. The benchmark CCSD(T)/CBS interaction energies have been obtained as described in Sec. III .

Generic image for table
Table X.

Mean unsigned relative errors (MURE, in percent) of the conventional and explicitly correlated MP2, CCSD, and (T) contributions to the interaction energy. The errors are averaged over the van der Waals minimum geometries for the seven dimers considered in this work. The benchmark CBS values have been obtained as described in Sec. III . The F12a and F12b triples corrections are identical.

Generic image for table
Table XI.

Median unsigned relative errors (MeURE, in percent) of different CCSD(T)/CCSD(T)-F12 variants and basis sets for the radial interaction energy curves of all seven complexes. The benchmark CCSD(T)/CBS interaction energies have been computed at the scaled-triples CCSD(T)-F12c/aQZM level.

Generic image for table
Table XII.

MP2-F12 and CCSD(T)-F12b interaction energies (in cm−1) for the near-minimum geometry of the He–CH4 complex, computed using several different choices of the correlation factor. The calculations in the first three columns employed a single Slater-type correlation factor fitted to six GTGs. The geminal exponent β was fixed at 1.0 (first column), taken as the recommended value from Ref. 86 (like in most calculations in this work, second column), or chosen to minimize the MP2-F12 interaction energy (third column). The calculations in the column marked “Optimized GTGs” utilized six GTGs with even-tempered exponents and coefficients obtained by minimizing the MP2-F12 interaction energy as described in the text. The diagonal 3C(FIX) Ansatz and the same DF/RI bases as in the rest of this work were used. The numbers in parentheses are the values of β. The benchmark MP2/CBS and CCSD(T)/CBS interaction energies amount to −22.283 and −29.425 cm−1, respectively.

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/content/aip/journal/jcp/138/15/10.1063/1.4800981
2013-04-16
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Basis set converged weak interaction energies from conventional and explicitly correlated coupled-cluster approach
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/15/10.1063/1.4800981
10.1063/1.4800981
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