Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

Vogiatzis, Konstantinos D.; Ma, Dongxia; Olsen, Jeppe; Gagliardi, Laura; de Jong, Wibe A.

doi:10.1063/1.4989858

Pushing configuration-interaction to the limit: Towards massively parallel MCSCF calculations

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4989858· OSTI ID:1436649

^[1]; Ma, Dongxia ^[2]; ^[3]; ^[4]; ^[5]

Univ. of Minnesota, Minneapolis, MN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Minnesota, Minneapolis, MN (United States); Max Planck Institut fur Festkorperforschung, Stuttgart (Germany)
Aarhus Univ., Aarhus C (Denmark)
Univ. of Minnesota, Minneapolis, MN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

A new large-scale parallel multiconfigurational self-consistent field (MCSCF) implementation in the open-source NWChem computational chemistry code is presented. The generalized active space approach is used to partition large configuration interaction (CI) vectors and generate a sufficient number of batches that can be distributed to the available cores. Massively parallel CI calculations with large active spaces can be performed. The new parallel MCSCF implementation is tested for the chromium trimer and for an active space of 20 electrons in 20 orbitals, which can now routinely be performed. Unprecedented CI calculations with an active space of 22 electrons in 22 orbitals for the pentacene systems were performed and a single CI iteration calculation with an active space of 24 electrons in 24 orbitals for the chromium tetramer was possible. In conclusion, the chromium tetramer corresponds to a CI expansion of one trillion Slater determinants (914 058 513 424) and is the largest conventional CI calculation attempted up to date.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: SC-22.1 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE

Grant/Contract Number:: AC02-05CH11231; SC0008666

OSTI ID:: 1436649

Alternate ID(s):: OSTI ID: 1420593

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 147; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

A massively parallel multireference configuration interaction program: The parallel COLUMBUS program Dachsel, Holger; Lischka, Hans; Shepard, Ron Journal of Computational Chemistry, Vol. 18, Issue 3 https://doi.org/10.1002/(sici)1096-987x(199702)18:3<430::aid-jcc12>3.0.co;2-m	journal	February 1997
Parallel internally contracted multireference configuration interaction Dobbyn, Abigail J.; Knowles, Peter J.; Harrison, Robert J. Journal of Computational Chemistry, Vol. 19, Issue 11 https://doi.org/10.1002/(sici)1096-987x(199808)19:11<1215::aid-jcc2>3.0.co;2-n	journal	August 1998
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K. Journal of Computational Chemistry, Vol. 37, Issue 5 https://doi.org/10.1002/jcc.24221	journal	November 2015
Methods of Electronic Structure Theory Schaefer, Henry F. Springer New York, NY https://doi.org/10.1007/978-1-4757-0887-5	book	January 1977
The Direct Configuration Interaction Method from Molecular Integrals Roos, Björn O.; Siegbahn, Per E. M. Methods of Electronic Structure Theory https://doi.org/10.1007/978-1-4757-0887-5_7	book	January 1977
A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory Horn, Shawn; Plasser, Felix; Müller, Thomas Highlights in Theoretical Chemistry https://doi.org/10.1007/978-3-662-48148-6_19	book	June 2014
Parallel algorithm for integral transformations and GUGA MCSCF Windus, Theresa L.; Schmidt, Michael W.; Gordon, Mark S. Theoretica Chimica Acta, Vol. 89, Issue 1 https://doi.org/10.1007/bf01167282	journal	September 1994
A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory Horn, Shawn; Plasser, Felix; Müller, Thomas Theoretical Chemistry Accounts, Vol. 133, Issue 8 https://doi.org/10.1007/s00214-014-1511-8	journal	June 2014
A new method for large-scale Cl calculations Roos, B. Chemical Physics Letters, Vol. 15, Issue 2 https://doi.org/10.1016/0009-2614(72)80140-4	journal	August 1972
Multi-root configuration interaction calculations Handy, N. C. Chemical Physics Letters, Vol. 74, Issue 2 https://doi.org/10.1016/0009-2614(80)85158-x	journal	September 1980
A new direct CI method for large CI expansions in a small orbital space Siegbahn, Per E. M. Chemical Physics Letters, Vol. 109, Issue 5 https://doi.org/10.1016/0009-2614(84)80336-x	journal	August 1984
A new determinant-based full configuration interaction method Knowles, P. J.; Handy, N. C. Chemical Physics Letters, Vol. 111, Issue 4-5 https://doi.org/10.1016/0009-2614(84)85513-x	journal	November 1984
Vectorizable approach to molecular CI problems using determinantal basis Zarrabian, S.; Sarma, C. R.; Paldus, J. Chemical Physics Letters, Vol. 155, Issue 2 https://doi.org/10.1016/0009-2614(89)85346-1	journal	February 1989
Passing the one-billion limit in full configuration-interaction (FCI) calculations Olsen, Jeppe; Jørgensen, Poul; Simons, Jack Chemical Physics Letters, Vol. 169, Issue 6 https://doi.org/10.1016/0009-2614(90)85633-n	journal	June 1990
The iterative calculation of a few of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices Davidson, Ernest R. Journal of Computational Physics, Vol. 17, Issue 1 https://doi.org/10.1016/0021-9991(75)90065-0	journal	January 1975
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
A parallel Full-CI algorithm Ansaloni, Roberto; Bendazzoli, Gian Luigi; Evangelisti, Stefano Computer Physics Communications, Vol. 128, Issue 1-2 https://doi.org/10.1016/s0010-4655(99)00542-1	journal	June 2000
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
Variational Optimization of the Second-Order Density Matrix Corresponding to a Seniority-Zero Configuration Interaction Wave Function Poelmans, Ward; Van Raemdonck, Mario; Verstichel, Brecht Journal of Chemical Theory and Computation, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jctc.5b00378	journal	August 2015
Stochastic Multiconfigurational Self-Consistent Field Theory Thomas, Robert E.; Sun, Qiming; Alavi, Ali Journal of Chemical Theory and Computation, Vol. 11, Issue 11 https://doi.org/10.1021/acs.jctc.5b00917	journal	October 2015
Combining the Complete Active Space Self-Consistent Field Method and the Full Configuration Interaction Quantum Monte Carlo within a Super-CI Framework, with Application to Challenging Metal-Porphyrins Li Manni, Giovanni; Smart, Simon D.; Alavi, Ali Journal of Chemical Theory and Computation, Vol. 12, Issue 3 https://doi.org/10.1021/acs.jctc.5b01190	journal	February 2016
Large-Scale Variational Two-Electron Reduced-Density-Matrix-Driven Complete Active Space Self-Consistent Field Methods Fosso-Tande, Jacob; Nguyen, Truong-Son; Gidofalvi, Gergely Journal of Chemical Theory and Computation, Vol. 12, Issue 5 https://doi.org/10.1021/acs.jctc.6b00190	journal	April 2016
Coupled-Cluster Valence-Bond Singles and Doubles for Strongly Correlated Systems: Block-Tensor Based Implementation and Application to Oligoacenes Lee, Joonho; Small, David W.; Epifanovsky, Evgeny Journal of Chemical Theory and Computation, Vol. 13, Issue 2 https://doi.org/10.1021/acs.jctc.6b01092	journal	January 2017
Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications Szalay, Péter G.; Müller, Thomas; Gidofalvi, Gergely Chemical Reviews, Vol. 112, Issue 1 https://doi.org/10.1021/cr200137a	journal	December 2011
Large-Scale Parallel Uncontracted Multireference-Averaged Quadratic Coupled Cluster: The Ground State of the Chromium Dimer Revisited ^† Müller, Thomas The Journal of Physical Chemistry A, Vol. 113, Issue 45 https://doi.org/10.1021/jp905254u	journal	November 2009
Dynamical and Nondynamical Correlation Mok, Daniel K. W.; Neumann, Ralf; Handy, Nicholas C. The Journal of Physical Chemistry, Vol. 100, Issue 15 https://doi.org/10.1021/jp9528020	journal	January 1996
Utilizing high performance computing for chemistry: parallel computational chemistry de Jong, Wibe A.; Bylaska, Eric; Govind, Niranjan Physical Chemistry Chemical Physics, Vol. 12, Issue 26 https://doi.org/10.1039/c002859b	journal	January 2010
Parallel implementation of the CI-vector evaluation in full CI/CAS-SCF Klene, Michael; Robb, Michael A.; Frisch, Michael J. The Journal of Chemical Physics, Vol. 113, Issue 14 https://doi.org/10.1063/1.1290014	journal	October 2000
The parallel implementation of a full configuration interaction program Gan, Zhengting; Alexeev, Yuri; Gordon, Mark S. The Journal of Chemical Physics, Vol. 119, Issue 1 https://doi.org/10.1063/1.1575193	journal	July 2003
Direct configuration interaction and multiconfigurational self-consistent-field method for multiple active spaces with variable occupations. I. Method Ivanic, Joseph The Journal of Chemical Physics, Vol. 119, Issue 18 https://doi.org/10.1063/1.1615954	journal	November 2003
Multireference correlation in long molecules with the quadratic scaling density matrix renormalization group Hachmann, Johannes; Cardoen, Wim; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 125, Issue 14 https://doi.org/10.1063/1.2345196	journal	October 2006
Large-scale parallel configuration interaction. I. Nonrelativistic and scalar-relativistic general active space implementation with application to (Rb–Ba)+ Knecht, Stefan; Jensen, Hans Jørgen Aa.; Fleig, Timo The Journal of Chemical Physics, Vol. 128, Issue 1 https://doi.org/10.1063/1.2805369	journal	January 2008
Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene Ghosh, Debashree; Hachmann, Johannes; Yanai, Takeshi The Journal of Chemical Physics, Vol. 128, Issue 14 https://doi.org/10.1063/1.2883976	journal	April 2008
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
Active-space two-electron reduced-density-matrix method: Complete active-space calculations without diagonalization of the N-electron Hamiltonian Gidofalvi, Gergely; Mazziotti, David A. The Journal of Chemical Physics, Vol. 129, Issue 13 https://doi.org/10.1063/1.2983652	journal	October 2008
Fermion Monte Carlo without fixed nodes: A game of life, death, and annihilation in Slater determinant space Booth, George H.; Thom, Alex J. W.; Alavi, Ali The Journal of Chemical Physics, Vol. 131, Issue 5 https://doi.org/10.1063/1.3193710	journal	January 2009
Large-scale parallel configuration interaction. II. Two- and four-component double-group general active space implementation with application to BiH Knecht, Stefan; Jensen, Hans Jørgen Aa.; Fleig, Timo The Journal of Chemical Physics, Vol. 132, Issue 1 https://doi.org/10.1063/1.3276157	journal	January 2010
The two faces of static correlation Hollett, Joshua W.; Gill, Peter M. W. The Journal of Chemical Physics, Vol. 134, Issue 11 https://doi.org/10.1063/1.3570574	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
Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces Olsen, Jeppe; Roos, Björn O.; Jo/rgensen, Poul The Journal of Chemical Physics, Vol. 89, Issue 4 https://doi.org/10.1063/1.455063	journal	August 1988
Semi-stochastic full configuration interaction quantum Monte Carlo: Developments and application Blunt, N. S.; Smart, Simon D.; Kersten, J. A. F. The Journal of Chemical Physics, Vol. 142, Issue 18 https://doi.org/10.1063/1.4920975	journal	May 2015
Left-right correlation energy Handy, Nicholas C.; Cohen, Aron J. Molecular Physics, Vol. 99, Issue 5 https://doi.org/10.1080/00268970010018431	journal	March 2001
Density matrix formulation for quantum renormalization groups White, Steven R. Physical Review Letters, Vol. 69, Issue 19 https://doi.org/10.1103/physrevlett.69.2863	journal	November 1992
The density-matrix renormalization group Schollwöck, U. Reviews of Modern Physics, Vol. 77, Issue 1 https://doi.org/10.1103/revmodphys.77.259	journal	April 2005
The Density Matrix Renormalization Group in Quantum Chemistry Chan, Garnet Kin-Lic; Sharma, Sandeep Annual Review of Physical Chemistry, Vol. 62, Issue 1 https://doi.org/10.1146/annurev-physchem-032210-103338	journal	May 2011
Advances, Applications and Performance of the Global Arrays Shared Memory Programming Toolkit Nieplocha, Jarek; Palmer, Bruce; Tipparaju, Vinod The International Journal of High Performance Computing Applications, Vol. 20, Issue 2 https://doi.org/10.1177/1094342006064503	journal	May 2006
Combining the Complete Active Space Self-Consistent Field Method and the Full Configuration Interaction Quantum Monte Carlo within a Super-CI Framework, with Application to Challenging Metal-Porphyrins Li Manni, Giovanni; Smart, Simon D.; Alavi, Ali Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.21652	text	January 2016
Stochastic Multiconfigurational Self-Consistent Field Theory. Thomas, Robert E.; Sun, Qiming; Alavi, Ali Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.21655	text	January 2015
Semi-stochastic full configuration interaction quantum Monte Carlo: developments and application Blunt, N. S.; Smart, Simon D.; Kersten, J. A. F. arXiv https://doi.org/10.48550/arxiv.1502.04847	text	January 2015
The density-matrix renormalization group Schollwoeck, Ulrich arXiv https://doi.org/10.48550/arxiv.cond-mat/0409292	text	January 2004
Multireference Correlation in Long Molecules with the Quadratic Scaling Density Matrix Renormalization Group Hachmann, Johannes; Cardoen, Wim; Chan, Garnet Kin-Lic arXiv https://doi.org/10.48550/arxiv.cond-mat/0606115	text	January 2006

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