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Correlated one-body potential from second-order Møller-Plesset perturbation theory: Alternative to orbital-optimized MP2 method
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10.1063/1.4809983
/content/aip/journal/jcp/138/22/10.1063/1.4809983
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4809983

Figures

Image of FIG. 1.
FIG. 1.

Deviations of the reaction energies of the MP2, OO-RI-MP2, and OB-MP2 methods with the cc-pVDZ (upper panel) and cc-pVTZ (lower panel) basis sets from the CCSD(T) reference data.

Image of FIG. 2.
FIG. 2.

Errors of the reaction energies of the OB-MP2-F12 method with the cc-pVDZ and cc-pVTZ basis sets in comparison with the CCSD(T)/cc-pVQZ values.

Image of FIG. 3.
FIG. 3.

Reference IPs versus minus HOMO energies (−ε) from HF, B3LYP, LC-wPBE, and OB-MP2 calculations as well as [Eq. (22a) ] for alkali metals (upper panel) and non-metallic molecules (lower panel). The straight line represents perfect correlation of measurements. The values in the parentheses inside the plots are the experimental IPs in units of eV (see Table IV for details).

Image of FIG. 4.
FIG. 4.

Reference EAs versus minus LUMO energies (−ε) from HF, B3LYP, LC-wPBE, and OB-MP2 calculations as well as [Eq. (22b) ] for alkali metals (upper panel) and non-metallic molecules excluding Ar and Ne gases (lower panel). The straight line represents perfect correlation of measurements. The values in the parentheses inside the plots are the experimental or vertical CCSD(T) EAs in units of eV (see Table IV for details).

Image of FIG. 5.
FIG. 5.

Energy levels of the valence orbital states (1 , 1 , , , 2 , and 2 ) of in the closed-shell singlet state Σ with various bond lengths: R(Fe–H) = 1.35, 1.40, 1.45, and 1.50 Å, calculated by the (a) HF, (b) PBE, and (c) OB-MP2 methods. (d) The 3D plots of the MOs from the OB-MP2 calculation. The bonding 1 and 1 orbitals and the nonbonding ( , , ) orbitals are doubly-occupied. The bonding and anti-bonding 2 and 2 orbitals are empty states.

Image of FIG. 6.
FIG. 6.

The 3D plots of the 2π( , , π*(NO)), , and orbitals of the CoNO molecule. They are doubly-occupied in the HF, B3LYP, and OB-MP2 calculations. Co, N, and O atoms are shown in purple, blue, and red, respectively.

Tables

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Table I.

Benchmark set of 25 reactions.

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Table II.

Statistical deviations of MP2, OO-RI-MP2, and OB-MP2 reaction energies from CCSD(T) reference data with the cc-pVDZ and cc-pVTZ basis sets. Maximum absolute deviation (MAX), difference between maximum and minimum absolute deviations ( ), root mean square (RMS), and mean absolute deviation (MAD) are shown in E.

Generic image for table
Table III.

Statistical performance (in E) against the reaction energies calculated with CCSD(T)/cc-pVQZ for the reaction set in Table I .

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Table IV.

Test molecules and reference IP and EA values (in eV) used for benchmark calculations. The experimental values are taken from Ref. . The values obtained at the CCSD(T)/cc-pVTZ level of theory are used for reference where experimental data are not available.

Generic image for table
Table V.

Subtraction of reference IPs from minus HOMO energies calculated by the HF, B3LYP, LC-wPBE, and OB-MP2 methods and the values of [Eq. (22a) ]. The units are in eV. The reference values are given in Table IV .

Generic image for table
Table VI.

Subtraction of reference EAs from minus LUMO energies calculated by the HF, B3LYP, LC-wPBE, and OB-MP2 methods and the values of [Eq. (22b) ]. The units are in eV. The reference values are given in Table IV .

Generic image for table
Table VII.

Orbital energies (in E) of the occupied orbital states 2π( , , π*(NO)), and (shown in Fig. 6 ) of CoNO from the HF, B3LYP, and OB-MP2 calculations.

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/content/aip/journal/jcp/138/22/10.1063/1.4809983
2013-06-13
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Correlated one-body potential from second-order Møller-Plesset perturbation theory: Alternative to orbital-optimized MP2 method
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/22/10.1063/1.4809983
10.1063/1.4809983
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