Communication: Towards ab initio self-energy embedding theory in quantum chemistry

Kananenka, Alexei A.; Zgid, Dominika

doi:10.1063/1.4938562

Title: Communication: Towards ab initio self-energy embedding theory in quantum chemistry

Journal Article · Mon Dec 28 00:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4938562· OSTI ID:22493359

Kananenka, Alexei A.; Zgid, Dominika ^[1]

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States)

The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.

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OSTI ID:: 22493359

Journal Information:: Journal of Chemical Physics, Vol. 143, Issue 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606

Country of Publication:: United States

Language:: English

References (39)

The Dalton quantum chemistry program system: The Dalton program Aidas, Kestutis; Angeli, Celestino; Bak, Keld L. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 3 https://doi.org/10.1002/wcms.1172	journal	September 2013
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
A modified definition of the zeroth-order Hamiltonian in multiconfigurational perturbation theory (CASPT2) Ghigo, Giovanni; Roos, Björn O.; Malmqvist, Per-Åke Chemical Physics Letters, Vol. 396, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.08.032	journal	September 2004
Systematic Expansion of Active Spaces beyond the CASSCF Limit: A GASSCF/SplitGAS Benchmark Study Vogiatzis, Konstantinos D.; Li Manni, Giovanni; Stoneburner, Samuel J. Journal of Chemical Theory and Computation, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jctc.5b00191	journal	June 2015
Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re ₂ Cl ₈ ^2– Carlson, Rebecca K.; Truhlar, Donald G.; Gagliardi, Laura Journal of Chemical Theory and Computation, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jctc.5b00609	journal	August 2015
SplitGAS Method for Strong Correlation and the Challenging Case of Cr ₂ Li Manni, Giovanni; Ma, Dongxia; Aquilante, Francesco Journal of Chemical Theory and Computation, Vol. 9, Issue 8 https://doi.org/10.1021/ct400046n	journal	July 2013
Multiconfiguration Pair-Density Functional Theory Li Manni, Giovanni; Carlson, Rebecca K.; Luo, Sijie Journal of Chemical Theory and Computation, Vol. 10, Issue 9 https://doi.org/10.1021/ct500483t	journal	August 2014
The restricted active space self-consistent-field method, implemented with a split graph unitary group approach Malmqvist, Per Aake.; Rendell, Alistair.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a011	journal	July 1990
Second-order perturbation theory with a CASSCF reference function Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a012	journal	July 1990
Introduction of n -electron valence states for multireference perturbation theory Angeli, C.; Cimiraglia, R.; Evangelisti, S. The Journal of Chemical Physics, Vol. 114, Issue 23 https://doi.org/10.1063/1.1361246	journal	June 2001
Combining multideterminantal wave functions with density functionals to handle near-degeneracy in atoms and molecules Pollet, R.; Savin, A.; Leininger, T. The Journal of Chemical Physics, Vol. 116, Issue 4 https://doi.org/10.1063/1.1430739	journal	January 2002
n -electron valence state perturbation theory: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants Angeli, Celestino; Cimiraglia, Renzo; Malrieu, Jean-Paul The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1515317	journal	November 2002
Gaussian Basis Functions for Use in Molecular Calculations. III. Contraction of (10s6p) Atomic Basis Sets for the First‐Row Atoms Dunning, Thom. H. The Journal of Chemical Physics, Vol. 55, Issue 2 https://doi.org/10.1063/1.1676139	journal	July 1971
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules Hehre, W. J.; Ditchfield, R.; Pople, J. A. The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261 https://doi.org/10.1063/1.1677527	journal	March 1972
Strongly Correlated Materials: Insights From Dynamical Mean-Field Theory Kotliar, Gabriel; Vollhardt, Dieter Physics Today, Vol. 57, Issue 3 https://doi.org/10.1063/1.1712502	journal	March 2004
The density matrix renormalization group self-consistent field method: Orbital optimization with the density matrix renormalization group method in the active space Zgid, Dominika; Nooijen, Marcel The Journal of Chemical Physics, Vol. 128, Issue 14 https://doi.org/10.1063/1.2883981	journal	April 2008
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems Malmqvist, Per Åke; Pierloot, Kristine; Shahi, Abdul Rehaman Moughal The Journal of Chemical Physics, Vol. 128, Issue 20 https://doi.org/10.1063/1.2920188	journal	May 2008
High-performance ab initio density matrix renormalization group method: Applicability to large-scale multireference problems for metal compounds Kurashige, Yuki; Yanai, Takeshi The Journal of Chemical Physics, Vol. 130, Issue 23 https://doi.org/10.1063/1.3152576	journal	June 2009
Strong correlation treated via effective hamiltonians and perturbation theory Li Manni, Giovanni; Aquilante, Francesco; Gagliardi, Laura The Journal of Chemical Physics, Vol. 134, Issue 3 https://doi.org/10.1063/1.3532927	journal	January 2011
Dynamical mean-field theory from a quantum chemical perspective Zgid, Dominika; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 134, Issue 9 https://doi.org/10.1063/1.3556707	journal	March 2011
The generalized active space concept in multiconfigurational self-consistent field methods Ma, Dongxia; Li Manni, Giovanni; Gagliardi, Laura The Journal of Chemical Physics, Vol. 135, Issue 4 https://doi.org/10.1063/1.3611401	journal	July 2011
Ab initio quantum chemistry using the density matrix renormalization group White, Steven R.; Martin, Richard L. The Journal of Chemical Physics, Vol. 110, Issue 9 https://doi.org/10.1063/1.478295	journal	March 1999
Communication: Active-space decomposition for molecular dimers Parker, Shane M.; Seideman, Tamar; Ratner, Mark A. The Journal of Chemical Physics, Vol. 139, Issue 2 https://doi.org/10.1063/1.4813827	journal	July 2013
Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory Phillips, Jordan J.; Zgid, Dominika The Journal of Chemical Physics, Vol. 140, Issue 24 https://doi.org/10.1063/1.4884951	journal	June 2014
Fractional charge and spin errors in self-consistent Green’s function theory Phillips, Jordan J.; Kananenka, Alexei A.; Zgid, Dominika The Journal of Chemical Physics, Vol. 142, Issue 19 https://doi.org/10.1063/1.4921259	journal	May 2015
Renormalization of myoglobin-ligand binding energetics by quantum many-body effects Weber, C.; Cole, D. J.; O'Regan, D. D. Proceedings of the National Academy of Sciences, Vol. 111, Issue 16 https://doi.org/10.1073/pnas.1322966111	journal	April 2014
Electronic structure calculations using dynamical mean field theory Held, K. Advances in Physics, Vol. 56, Issue 6 https://doi.org/10.1080/00018730701619647	journal	November 2007
Development of a CAS-DFT method covering non-dynamical and dynamical electron correlation in a balanced way Gräfenstein, Jürgen; Cremer *, Dieter Molecular Physics, Vol. 103, Issue 2-3 https://doi.org/10.1080/00268970512331318858	journal	January 2005
Dynamical mean field theory for diatomic molecules and the exact double counting Lee, Juho; Haule, Kristjan Physical Review B, Vol. 91, Issue 15 https://doi.org/10.1103/physrevb.91.155144	journal	April 2015
FLEX+DMFT approach to the $d$ -wave superconducting phase diagram of the two-dimensional Hubbard model Kitatani, Motoharu; Tsuji, Naoto; Aoki, Hideo Physical Review B, Vol. 92, Issue 8 https://doi.org/10.1103/physrevb.92.085104	journal	August 2015
Combined GW and dynamical mean-field theory: Dynamical screening effects in transition metal oxides Tomczak, Jan M.; Casula, Michele; Miyake, Takashi EPL (Europhysics Letters), Vol. 100, Issue 6 https://doi.org/10.1209/0295-5075/100/67001	journal	December 2012
Finite-Temperature Magnetism of Transition Metals: An ab initio Dynamical Mean-Field Theory Katsnelson, M. I.; Kotliar, G.; Lichtenstein, A. I. The American Physical Society https://doi.org/10.17877/de290r-10620	text	January 2001
Dynamical mean-field theory from a quantum chemical perspective Zgid, Dominika; Chan, Garnet Kin-Lic arXiv https://doi.org/10.48550/arxiv.1012.3609	text	January 2010
Truncated Configuration Interaction expansions as solvers for correlated quantum impurity models and dynamical mean field theory Zgid, Dominika; Gull, Emanuel; Chan, Garnet arXiv https://doi.org/10.48550/arxiv.1203.1914	text	January 2012
Importance of many body effects in the kernel of hemoglobin for ligand binding Weber, Cedric; O'Regan, David D.; Hine, Nicholas D. M. arXiv https://doi.org/10.48550/arxiv.1206.0412	text	January 2012
Systematically improvable multi-scale solver for correlated electron systems Kananenka, Alexei A.; Gull, Emanuel; Zgid, Dominika arXiv https://doi.org/10.48550/arxiv.1410.5118	text	January 2014
Density functional versus spin-density functional and the choice of correlated subspace in multi-variable effective action theories of electronic structure Park, Hyowon; Millis, Andrew J.; Marianetti, Chris A. arXiv https://doi.org/10.48550/arxiv.1505.00227	preprint	January 2015
Electronic Structure Calculations using Dynamical Mean Field Theory Held, K. arXiv https://doi.org/10.48550/arxiv.cond-mat/0511293	text	January 2005
Dynamical mean-field theory using Wannier functions: a flexible route to electronic structure calculations of strongly correlated materials Lechermann, F.; Georges, A.; Poteryaev, A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0605539	text	January 2006

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