Automatic Partition of Orbital Spaces Based on Singular Value Decomposition in the Context of Embedding Theories

Claudino, Daniel; Mayhall, Nicholas J.

doi:10.1021/acs.jctc.8b01112

Title: Automatic Partition of Orbital Spaces Based on Singular Value Decomposition in the Context of Embedding Theories

Journal Article · 07 January 2019 · Journal of Chemical Theory and Computation

DOI: https://doi.org/10.1021/acs.jctc.8b01112 · OSTI ID:1631164

^[1];

^[2]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Virginia Tech
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Here, we present a simple approach for orbital space partitioning to be employed in the projection-based embedding theory developed by Goodpaster and co-workers [Manby et al. J. Chem. Theory Comput. 2012, 8, 2564]. Once the atoms are assigned to the desired subspaces, the molecular orbitals are projected onto the atomic orbitals centered on active atoms and then singular value decomposed. The right singular vectors are used to rotate the initial molecular orbitals, taking the largest gap in the singular values spectrum to define the most suitable partition of the occupied orbital space. This scheme is free from numerical parameters, contrary to the Mulliken charge threshold or the completeness criterion previously used. The performance of this new prescription is assessed in a test set of several distinct reactions, the deprotonation of decanoic acid, the Diels-Alder reaction of 1,3-butadiene and octadecanonaene, the torsional potential of a retinal derivative, and the critical points along the reaction coordinate of an instance of the Menshutkin S_N2 reaction inside a carbon nanotube.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018326

OSTI ID:: 1631164

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 15; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Comparison of the boys and Pipek-Mezey localizations in the local correlation approach and automatic virtual basis selection Boughton, James W.; Pulay, Peter Journal of Computational Chemistry, Vol. 14, Issue 6 https://doi.org/10.1002/jcc.540140615	journal	June 1993
IMOMM: A new integratedab initio + molecular mechanics geometry optimization scheme of equilibrium structures and transition states Maseras, Feliu; Morokuma, Keiji Journal of Computational Chemistry, Vol. 16, Issue 9 https://doi.org/10.1002/jcc.540160911	journal	September 1995
Embedding Methods in Quantum Chemistry Goez, Albrecht; Neugebauer, Johannes Frontiers of Quantum Chemistry https://doi.org/10.1007/978-981-10-5651-2_7	book	November 2017
The influence of polarization functions on molecular orbital hydrogenation energies Hariharan, P. C.; Pople, J. A. Theoretica Chimica Acta, Vol. 28, Issue 3 https://doi.org/10.1007/BF00533485	journal	January 1973
Open-shell analytical energy gradients for triple excitation many-body, coupled-cluster methods: MBPT(4), CCSD+T(CCSD), CCSD(T),and QCISD(T) Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J. Chemical Physics Letters, Vol. 200, Issue 1-2 https://doi.org/10.1016/0009-2614(92)87036-O	journal	November 1992
Use of approximate integrals in ab initio theory. An application in MP2 energy calculations Feyereisen, Martin; Fitzgerald, George; Komornicki, Andrew Chemical Physics Letters, Vol. 208, Issue 5-6 https://doi.org/10.1016/0009-2614(93)87156-W	journal	June 1993
Integral approximations for LCAO-SCF calculations Vahtras, O.; Almlöf, J.; Feyereisen, M. W. Chemical Physics Letters, Vol. 213, Issue 5-6 https://doi.org/10.1016/0009-2614(93)89151-7	journal	October 1993
Theoretical studies of enzymic reactions: Dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme Warshel, A.; Levitt, M. Journal of Molecular Biology, Vol. 103, Issue 2 https://doi.org/10.1016/0022-2836(76)90311-9	journal	May 1976
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/S0009-2614(89)87395-6	journal	May 1989
A Projector-Embedding Approach for Multiscale Coupled-Cluster Calculations Applied to Citrate Synthase Bennie, Simon J.; van der Kamp, Marc W.; Pennifold, Robert C. R. Journal of Chemical Theory and Computation, Vol. 12, Issue 6 https://doi.org/10.1021/acs.jctc.6b00285	journal	May 2016
A Practical Guide to Density Matrix Embedding Theory in Quantum Chemistry Wouters, Sebastian; Jiménez-Hoyos, Carlos A.; Sun, Qiming Journal of Chemical Theory and Computation, Vol. 12, Issue 6 https://doi.org/10.1021/acs.jctc.6b00316	journal	May 2016
Theory and Applications of Generalized Pipek–Mezey Wannier Functions Jónsson, Elvar Ö.; Lehtola, Susi; Puska, Martti Journal of Chemical Theory and Computation, Vol. 13, Issue 2 https://doi.org/10.1021/acs.jctc.6b00809	journal	January 2017
Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability Parrish, Robert M.; Burns, Lori A.; Smith, Daniel G. A. Journal of Chemical Theory and Computation, Vol. 13, Issue 7 https://doi.org/10.1021/acs.jctc.7b00174	journal	June 2017
Dual Basis Set Approach for Density Functional and Wave Function Embedding Schemes Hégely, Bence; Nagy, Péter R.; Kállay, Mihály Journal of Chemical Theory and Computation, Vol. 14, Issue 9 https://doi.org/10.1021/acs.jctc.8b00350	journal	July 2018
Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies Bennie, Simon J.; Curchod, Basile F. E.; Manby, Frederick R. The Journal of Physical Chemistry Letters, Vol. 8, Issue 22 https://doi.org/10.1021/acs.jpclett.7b02500	journal	November 2017
Breaking the Correlation between Energy Costs and Kinetic Barriers in Hydrogen Evolution via a Cobalt Pyridine-Diimine-Dioxime Catalyst Huo, Pengfei; Uyeda, Christopher; Goodpaster, Jason D. ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01387	journal	August 2016
Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO ₂ Reduction Chapovetsky, Alon; Welborn, Matthew; Luna, John M. ACS Central Science, Vol. 4, Issue 3 https://doi.org/10.1021/acscentsci.7b00607	journal	February 2018
Embedded Correlated Wavefunction Schemes: Theory and Applications Libisch, Florian; Huang, Chen; Carter, Emily A. Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar500086h	journal	May 2014
Frozen-Density Embedding Strategy for Multilevel Simulations of Electronic Structure Wesolowski, Tomasz A.; Shedge, Sapana; Zhou, Xiuwen Chemical Reviews, Vol. 115, Issue 12 https://doi.org/10.1021/cr500502v	journal	April 2015
Charge Transfer Across ONIOM QM:QM Boundaries: The Impact of Model System Preparation Mayhall, Nicholas J.; Raghavachari, Krishnan Journal of Chemical Theory and Computation, Vol. 6, Issue 10 https://doi.org/10.1021/ct1004164	journal	September 2010
A Simple, Exact Density-Functional-Theory Embedding Scheme Manby, Frederick R.; Stella, Martina; Goodpaster, Jason D. Journal of Chemical Theory and Computation, Vol. 8, Issue 8 https://doi.org/10.1021/ct300544e	journal	July 2012
Density Matrix Embedding: A Strong-Coupling Quantum Embedding Theory Knizia, Gerald; Chan, Garnet Kin-Lic Journal of Chemical Theory and Computation, Vol. 9, Issue 3 https://doi.org/10.1021/ct301044e	journal	February 2013
Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts Knizia, Gerald Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400687b	journal	October 2013
Pipek–Mezey Orbital Localization Using Various Partial Charge Estimates Lehtola, Susi; Jónsson, Hannes Journal of Chemical Theory and Computation, Vol. 10, Issue 2 https://doi.org/10.1021/ct401016x	journal	January 2014
Embedded Mean-Field Theory Fornace, Mark E.; Lee, Joonho; Miyamoto, Kaito Journal of Chemical Theory and Computation, Vol. 11, Issue 2 https://doi.org/10.1021/ct5011032	journal	January 2015
Calculation of .pi..pi.* excited state conformations and vibronic structure of retinal and related molecules Warshel, A.; Karplus, M. Journal of the American Chemical Society, Vol. 96, Issue 18 https://doi.org/10.1021/ja00825a001	journal	September 1974
Probing the Rhodopsin Cavity with Reduced Retinal Models at the CASPT2//CASSCF/AMBER Level of Theory Ferré, Nicolas; Olivucci, Massimo Journal of the American Chemical Society, Vol. 125, Issue 23 https://doi.org/10.1021/ja035087d	journal	June 2003
Calculating Hyperfine Couplings in Large Ionic Crystals Containing Hundreds of QM Atoms: Subsystem DFT Is the Key Kevorkyants, Ruslan; Wang, Xiqiao; Close, David M. The Journal of Physical Chemistry B, Vol. 117, Issue 45 https://doi.org/10.1021/jp405154d	journal	October 2013
Ab Initio Characterization of the Electrochemical Stability and Solvation Properties of Condensed-Phase Ethylene Carbonate and Dimethyl Carbonate Mixtures Barnes, Taylor A.; Kaminski, Jakub W.; Borodin, Oleg The Journal of Physical Chemistry C, Vol. 119, Issue 8 https://doi.org/10.1021/jp510882g	journal	January 2015
ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P( t -Bu) ₃ ) ₂ + H ₂ Oxidative Addition Svensson, Mats; Humbel, Stéphane; Froese, Robert D. J. The Journal of Physical Chemistry, Vol. 100, Issue 50 https://doi.org/10.1021/jp962071j	journal	January 1996
Implications of Torsional Potential of Retinal Isomers for Visual Excitation Honig, Barry; Karplus, Martin Nature, Vol. 229, Issue 5286 https://doi.org/10.1038/229558a0	journal	February 1971
Structure of the intersection space associated with Z/E photoisomerization of retinal in rhodopsin proteins Migani, Annapaola; Sinicropi, Adalgisa; Ferré, Nicolas Faraday Discuss., Vol. 127 https://doi.org/10.1039/B315217K	journal	January 2004
Optimization of auxiliary basis sets for RI-MP2 and RI-CC2 calculations: Core–valence and quintuple-ζ basis sets for H to Ar and QZVPP basis sets for Li to Kr Hättig, Christof Phys. Chem. Chem. Phys., Vol. 7, Issue 1 https://doi.org/10.1039/B415208E	journal	January 2005
Spin–flip non-orthogonal configuration interaction: a variational and almost black-box method for describing strongly correlated molecules Mayhall, Nicholas J.; Horn, Paul R.; Sundstrom, Eric J. Phys. Chem. Chem. Phys., Vol. 16, Issue 41 https://doi.org/10.1039/C4CP02818J	journal	January 2014
A fully direct RI-HF algorithm: Implementation, optimised auxiliary basis sets, demonstration of accuracy and efficiency Weigend, Florian Physical Chemistry Chemical Physics, Vol. 4, Issue 18 https://doi.org/10.1039/b204199p	journal	August 2002
Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations Weigend, Florian; Köhn, Andreas; Hättig, Christof The Journal of Chemical Physics, Vol. 116, Issue 8 https://doi.org/10.1063/1.1445115	journal	February 2002
Theory of Separability of Many‐Electron Systems Huzinaga, S.; Cantu, A. A. The Journal of Chemical Physics, Vol. 55, Issue 12 https://doi.org/10.1063/1.1675720	journal	December 1971
Coulombic potential energy integrals and approximations Whitten, J. L. The Journal of Chemical Physics, Vol. 58, Issue 10 https://doi.org/10.1063/1.1679012	journal	May 1973
Localized molecular orbitals for polyatomic molecules. I. A comparison of the Edmiston‐Ruedenberg and Boys localization methods Kleier, Daniel A.; Halgren, Thomas A.; Hall, John H. The Journal of Chemical Physics, Vol. 61, Issue 10 https://doi.org/10.1063/1.1681683	journal	November 1974
QM:QM electronic embedding using Mulliken atomic charges: Energies and analytic gradients in an ONIOM framework Hratchian, Hrant P.; Parandekar, Priya V.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 128, Issue 3 https://doi.org/10.1063/1.2814164	journal	January 2008
ONIOM-based QM:QM electronic embedding method using Löwdin atomic charges: Energies and analytic gradients Mayhall, Nicholas J.; Raghavachari, Krishnan; Hratchian, Hrant P. The Journal of Chemical Physics, Vol. 132, Issue 11 https://doi.org/10.1063/1.3315417	journal	March 2010
On some approximations in applications of X α theory Dunlap, B. I.; Connolly, J. W. D.; Sabin, J. R. The Journal of Chemical Physics, Vol. 71, Issue 8 https://doi.org/10.1063/1.438728	journal	October 1979
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples Purvis, George D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 76, Issue 4 https://doi.org/10.1063/1.443164	journal	February 1982
Towards a full CCSDT model for electron correlation Urban, Miroslav; Noga, Jozef; Cole, Samuel J. The Journal of Chemical Physics, Vol. 83, Issue 8 https://doi.org/10.1063/1.449067	journal	October 1985
Natural population analysis Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank The Journal of Chemical Physics, Vol. 83, Issue 2 https://doi.org/10.1063/1.449486	journal	July 1985
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions Pipek, János; Mezey, Paul G. The Journal of Chemical Physics, Vol. 90, Issue 9 https://doi.org/10.1063/1.456588	journal	May 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
The IMOMO method: Integration of different levels of molecular orbital approximations for geometry optimization of large systems: Test for n ‐butane conformation and S _N 2 reaction: RCl+Cl ⁻ Humbel, Stéphane; Sieber, Stefan; Morokuma, Keiji The Journal of Chemical Physics, Vol. 105, Issue 5 https://doi.org/10.1063/1.472065	journal	August 1996
Orbital localization using fourth central moment minimization Høyvik, Ida-Marie; Jansik, Branislav; Jørgensen, Poul The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4769866	journal	December 2012
Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes Goodpaster, Jason D.; Barnes, Taylor A.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4770226	journal	December 2012
Accurate basis set truncation for wavefunction embedding Barnes, Taylor A.; Goodpaster, Jason D.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 139, Issue 2 https://doi.org/10.1063/1.4811112	journal	July 2013
Accurate and systematically improvable density functional theory embedding for correlated wavefunctions Goodpaster, Jason D.; Barnes, Taylor A.; Manby, Frederick R. The Journal of Chemical Physics, Vol. 140, Issue 18 https://doi.org/10.1063/1.4864040	journal	May 2014
Accelerating wavefunction in density-functional-theory embedding by truncating the active basis set Bennie, Simon J.; Stella, Martina; Miller, Thomas F. The Journal of Chemical Physics, Vol. 143, Issue 2 https://doi.org/10.1063/1.4923367	journal	July 2015
Density matrix embedding in an antisymmetrized geminal power bath Tsuchimochi, Takashi; Welborn, Matthew; Van Voorhis, Troy The Journal of Chemical Physics, Vol. 143, Issue 2 https://doi.org/10.1063/1.4926650	journal	July 2015
Communication: Towards ab initio self-energy embedding theory in quantum chemistry Lan, Tran Nguyen; Kananenka, Alexei A.; Zgid, Dominika The Journal of Chemical Physics, Vol. 143, Issue 24 https://doi.org/10.1063/1.4938562	journal	December 2015
Exact density functional and wave function embedding schemes based on orbital localization Hégely, Bence; Nagy, Péter R.; Ferenczy, György G. The Journal of Chemical Physics, Vol. 145, Issue 6 https://doi.org/10.1063/1.4960177	journal	August 2016
Bootstrap embedding: An internally consistent fragment-based method Welborn, Matthew; Tsuchimochi, Takashi; Van Voorhis, Troy The Journal of Chemical Physics, Vol. 145, Issue 7 https://doi.org/10.1063/1.4960986	journal	August 2016
Communication: Density functional theory embedding with the orthogonality constrained basis set expansion procedure Culpitt, Tanner; Brorsen, Kurt R.; Hammes-Schiffer, Sharon The Journal of Chemical Physics, Vol. 146, Issue 21 https://doi.org/10.1063/1.4984777	journal	June 2017
Reduced scaling CASPT2 using supporting subspaces and tensor hyper-contraction Song, Chenchen; Martínez, Todd J. The Journal of Chemical Physics, Vol. 149, Issue 4 https://doi.org/10.1063/1.5037283	journal	July 2018
Even-handed subsystem selection in projection-based embedding Welborn, Matthew; Manby, Frederick R.; Miller, Thomas F. The Journal of Chemical Physics, Vol. 149, Issue 14 https://doi.org/10.1063/1.5050533	journal	October 2018
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Density Matrix Embedding: A Simple Alternative to Dynamical Mean-Field Theory Knizia, Gerald; Chan, Garnet Kin-Lic Physical Review Letters, Vol. 109, Issue 18 https://doi.org/10.1103/PhysRevLett.109.186404	journal	November 2012
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Construction of Some Molecular Orbitals to Be Approximately Invariant for Changes from One Molecule to Another Boys, S. F. Reviews of Modern Physics, Vol. 32, Issue 2 https://doi.org/10.1103/RevModPhys.32.296	journal	April 1960

Cited By (3)

Absolutely Localized Projection-Based Embedding for Excited States Wen, Xuelan; Graham, Daniel S.; Chulhai, Dhabih V. arXiv https://doi.org/10.48550/arxiv.1909.12423	preprint	January 2019
Regional Embedding Enables High-Level Quantum Chemistry for Surface Science Lau, Bryan T. G.; Knizia, Gerald; Berkelbach, Timothy C. arXiv https://doi.org/10.48550/arxiv.2010.00527	preprint	January 2020
Direct orbital selection for projection-based embedding Bensberg, Moritz; Neugebauer, Johannes The Journal of Chemical Physics, Vol. 150, Issue 21 https://doi.org/10.1063/1.5099007	journal	June 2019

Similar Records

1,3-Diferrocenyl-1,3-alkadienes in diene synthesis reactions

Journal Article · 1987 · J. Gen. Chem. USSR (Engl. Transl.); (United States) · OSTI ID:7005189

Pushin, A N; Klimova, E I; Sazanova, V A

Simple and Efficient Truncation of Virtual Spaces in Embedded Wave Functions via Concentric Localization

Journal Article · 2019 · Journal of Chemical Theory and Computation · OSTI ID:1631165

Claudino, Daniel; Mayhall, Nicholas J.

Theoretical study of the Diels-Alder reactions of zirconium dimer with ethylene and butadiene

Journal Article · 1995 · Journal of Physical Chemistry · OSTI ID:36626

Roszak, S; Balasubramanian, K

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Automatic Partition of Orbital Spaces Based on Singular Value Decomposition in the Context of Embedding Theories

Citation Formats

References (67)

Cited By (3)

Similar Records

Related Subjects