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Title: Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction

Authors:
ORCiD logo [1];  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720, USA, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1279020
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 5; Related Information: CHORUS Timestamp: 2018-05-11 11:36:25; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Yost, Shane R., and Head-Gordon, Martin. Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction. United States: N. p., 2016. Web. doi:10.1063/1.4959794.
Yost, Shane R., & Head-Gordon, Martin. Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction. United States. doi:10.1063/1.4959794.
Yost, Shane R., and Head-Gordon, Martin. Sun . "Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction". United States. doi:10.1063/1.4959794.
@article{osti_1279020,
title = {Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction},
author = {Yost, Shane R. and Head-Gordon, Martin},
abstractNote = {},
doi = {10.1063/1.4959794},
journal = {Journal of Chemical Physics},
number = 5,
volume = 145,
place = {United States},
year = {Sun Aug 07 00:00:00 EDT 2016},
month = {Sun Aug 07 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4959794

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  • In this paper we introduce two size consistent forms of the non-orthogonal configuration interaction with second-order Møller-Plesset perturbation theory method, NOCI-MP2. We show that the original NOCI-MP2 formulation [S. R. Yost, T. Kowalczyk, and T. VanVoorh, J. Chem. Phys. 193, 174104 (2013)], which is a perturb-then-diagonalize multi-reference method, is not size consistent. We also show that this causes significant errors in large systems like the linear acenes. By contrast, the size consistent versions of the method give satisfactory results for singlet and triplet excited states when compared to other multi-reference methods that include dynamic correlation. For NOCI-MP2 however, the numbermore » of required determinants to yield similar levels of accuracy is significantly smaller. These results show the promise of the NOCI-MP2 method, though work still needs to be done in creating a more consistent black-box approach to computing the determinants that comprise the many-electron NOCI basis.« less
  • Ground configuration and low-lying levels of Al-like ions contribute to a variety of laboratory and solar spectra, but the available information in databases are neither complete not necessarily correct. We have performed multireference Moeller-Plesset perturbation theory calculations that approach spectroscopic accuracy in order to check the information that databases hold on the 40 lowest levels of Al-Like ions of iron group elements (K through Ge), and to provide input for the interpretation of concurrent experiments. Our results indicate problems of the database holdings on the levels of the lowest quartet levels in the lighter elements of the range studied. Themore » results of our calculations of the decay rates of five long-lived levels (3s{sup 2}3p {sup 2}p{sup o}{sub 3/2}, 3s3p{sup 2} {sup 4}P{sup o} J and 3s3p3d {sup 4}F{sup o}{sub 9/2}) are compared with lifetime data from beam-foil, electron beam ion trap and heavy-ion storage ring experiments.« less
  • A combined quantum mechanical/molecular mechanical/continuum (QM/MM/C) style second order Møller-Plesset perturbation theory (MP2) method that incorporates induced dipole polarizable force field and induced surface charge continuum solvation model is established. The Z-vector method is modified to include induced dipoles and induced surface charges to determine the MP2 response density matrix, which can be used to evaluate MP2 properties. In particular, analytic nuclear gradient is derived and implemented for this method. Using the Assisted Model Building with Energy Refinement induced dipole polarizable protein force field, the QM/MM/C style MP2 method is used to study the hydrogen bonding distances and strengths ofmore » the photoactive yellow protein chromopore in the wild type and the Glu46Gln mutant.« less
  • General analytic gradient expressions (with the frozen-core approximation) are presented for density-fitted post-HF methods. An efficient implementation of frozen-core analytic gradients for the second-order Møller–Plesset perturbation theory (MP2) with the density-fitting (DF) approximation (applying to both reference and correlation energies), which is denoted as DF-MP2, is reported. The DF-MP2 method is applied to a set of alkanes, conjugated dienes, and noncovalent interaction complexes to compare the computational cost of single point analytic gradients with MP2 with the resolution of the identity approach (RI-MP2) [F. Weigend and M. Häser, Theor. Chem. Acc. 97, 331 (1997); R. A. Distasio, R. P. Steele,more » Y. M. Rhee, Y. Shao, and M. Head-Gordon, J. Comput. Chem. 28, 839 (2007)]. In the RI-MP2 method, the DF approach is used only for the correlation energy. Our results demonstrate that the DF-MP2 method substantially accelerate the RI-MP2 method for analytic gradient computations due to the reduced input/output (I/O) time. Because in the DF-MP2 method the DF approach is used for both reference and correlation energies, the storage of 4-index electron repulsion integrals (ERIs) are avoided, 3-index ERI tensors are employed instead. Further, as in case of integrals, our gradient equation is completely avoid construction or storage of the 4-index two-particle density matrix (TPDM), instead we use 2- and 3-index TPDMs. Hence, the I/O bottleneck of a gradient computation is significantly overcome. Therefore, the cost of the generalized-Fock matrix (GFM), TPDM, solution of Z-vector equations, the back transformation of TPDM, and integral derivatives are substantially reduced when the DF approach is used for the entire energy expression. Further application results show that the DF approach introduce negligible errors for closed-shell reaction energies and equilibrium bond lengths.« less