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Title: Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4986975· OSTI ID:1474039
 [1];  [1]; ORCiD logo [1];  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
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In earlier work [A. Y. Sokolov and G. K.-L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N-electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual internally contracted perturbation formulation and (ii) yielded the fully uncontracted NEVPT2 energy. We present a combination of t-NEVPT2 with a matrix product state (MPS) reference wavefunction (t-MPS-NEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the time-dependent density matrix renormalization group algorithm. In addition, we report a low-scaling MPS-based implementation of strongly contracted NEVPT2 (sc-MPS-NEVPT2) that avoids computation of the four-particle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the low-lying excited states in all-trans polyenes (C4H6 to C24H26), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals

Research Organization:
Princeton Univ., NJ (United States); California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Contributing Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Grant/Contract Number:
SC0008624; SC0010530; AC02-05CH11231
OSTI ID:
1474039
Alternate ID(s):
OSTI ID: 1365432
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 24; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

References (93)

A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions journal May 2016
Electronic excitations in long polyenes revisited journal March 2012
Complete vs Restricted Active Space Perturbation Theory Calculation of the Cr 2 Potential Energy Surface journal April 2011
Communication: A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states journal September 2014
Photosynthetic Light Harvesting by Carotenoids: Detection of an Intermediate Excited State journal December 2002
Multiconfigurational perturbation theory with level shift — the Cr2 potential revisited journal October 1995
Fully Internally Contracted Multireference Configuration Interaction Theory Using Density Matrix Renormalization Group: A Reduced-Scaling Implementation Derived by Computer-Aided Tensor Factorization journal October 2015
Relativistic Hamiltonians for Chemistry: A Primer journal November 2011
Communication: DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen) journal June 2014
The 2  1 A g state of trans,trans ‐1,3,5,7‐octatetraene in free jet expansions journal March 1993
Negative ion photoelectron spectroscopy of chromium dimer journal January 1993
Multireference Configuration Interaction Calculations on Cr 2 :  Passing the One Billion Limit in MRCI/MRACPF Calculations journal January 1999
Fluorescence from the 1  1 B u state of t r a n s , t r a n s ‐1,3,5,7‐octatetraene in a free jet journal August 1984
Entangled quantum electronic wavefunctions of the Mn4CaO5 cluster in photosystem II journal June 2013
Polyene spectroscopy: The lowest energy excited singlet state of diphenyloctatetraene and other linear polyenes journal November 1973
Finite-temperature density matrix renormalization using an enlarged Hilbert space journal December 2005
100 eV electron impact study of 1,3‐butadiene journal September 1981
Multireference configuration interaction theory using cumulant reconstruction with internal contraction of density matrix renormalization group wave function journal July 2013
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
The π→π* excited states of long linear polyenes studied by the CASCI-MRMP method journal December 2004
Fast linear scaling second-order Møller-Plesset perturbation theory (MP2) using local and density fitting approximations journal May 2003
Complete set of solutions of multireference coupled-cluster equations: The state-universal formalism journal April 2000
Introduction of n -electron valence states for multireference perturbation theory journal June 2001
Second‐order perturbation theory with a complete active space self‐consistent field reference function journal January 1992
Ab initio quantum chemistry using the density matrix renormalization group journal March 1999
The 2  1 A g state in the linear polyene 2,4,6,8,10,12,14,16‐octadecaoctaene journal November 1988
An efficient internally contracted multiconfiguration–reference configuration interaction method journal November 1988
Second-order perturbation theory with a density matrix renormalization group self-consistent field reference function: Theory and application to the study of chromium dimer journal September 2011
Large-Scale Parallel Uncontracted Multireference-Averaged Quadratic Coupled Cluster: The Ground State of the Chromium Dimer Revisited † journal November 2009
The density matrix renormalization group for ab initio quantum chemistry journal September 2014
The density-matrix renormalization group journal April 2005
Direct absorption spectroscopy of jet‐cooled polyenes. I. The 1  1 B + u ←1  1 A − g transition of t r a n s , t r a n s ‐1,3,5,7‐octatetraene journal November 1984
The lowest singlet states of octatetraene revisited journal May 2011
The Density Matrix Renormalization Group in Quantum Chemistry journal May 2011
The CIPT2 method: Coupling of multi-reference configuration interaction and multi-reference perturbation theory. Application to the chromium dimer journal November 2004
Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program
  • Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4 https://doi.org/10.1002/wcms.93
journal October 2011
High-performance ab initio density matrix renormalization group method: Applicability to large-scale multireference problems for metal compounds journal June 2009
Free‐jet fluorescence excitation spectrum of t r a n s , t r a n s ‐1,3,5,7‐octatetraene journal November 1981
The first detection of the 3A g − state in carotenoids using resonance-Raman excitation profiles journal April 2002
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn journal August 2005
Qualitative intruder-state problems in effective Hamiltonian theory and their solution through intermediate Hamiltonians journal June 1987
Electron impact study of the energy levels of t r a n s ‐1,3‐butadiene: II. Detailed analysis of valence and Rydberg transitions journal October 1980
Multireference Perturbation Theory with Cholesky Decomposition for the Density Matrix Renormalization Group journal February 2017
Third-order multireference perturbation theory The CASPT3 method journal October 1996
The Cr2 potential curve: a multireference pair functional treatment journal June 1996
Canonical transformation theory from extended normal ordering journal September 2007
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
State-specific multireference coupled-cluster theory: State-specific multireference coupled-cluster theory
  • Köhn, Andreas; Hanauer, Matthias; Mück, Leonie Anna
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 3, Issue 2 https://doi.org/10.1002/wcms.1120
journal October 2012
Fermion Monte Carlo without fixed nodes: A game of life, death, and annihilation in Slater determinant space journal January 2009
The low‐lying electronic excitations in long polyenes: A PPP‐MRD‐CI study journal December 1986
A driven similarity renormalization group approach to quantum many-body problems journal August 2014
Matrix product operators, matrix product states, and ab initio density matrix renormalization group algorithms journal July 2016
Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts journal October 2013
Interaction-round-a-face density-matrix renormalization-group method applied to rotational-invariant quantum spin chains journal March 2000
A state-specific partially internally contracted multireference coupled cluster approach journal June 2011
A study of cumulant approximations to n-electron valence multireference perturbation theory journal May 2009
Low-order scaling local electron correlation methods. IV. Linear scaling local coupled-cluster (LCCSD) journal January 2001
New electron correlation theories for transition metal chemistry journal January 2011
N -Electron Valence State Perturbation Theory Based on a Density Matrix Renormalization Group Reference Function, with Applications to the Chromium Dimer and a Trimer Model of Poly( p -Phenylenevinylene) journal March 2016
Electronic excitations in finite and infinite polyenes journal September 1987
An orbital-invariant internally contracted multireference coupled cluster approach journal March 2011
Canonical transformation theory for multireference problems journal May 2006
Spin-adapted density matrix renormalization group algorithms for quantum chemistry journal March 2012
The choice of a zeroth‐order Hamiltonian for second‐order perturbation theory with a complete active space self‐consistent‐field reference function journal March 1995
The electronic spectrum of Cr2 journal May 1995
An auxiliary-field quantum Monte Carlo study of the chromium dimer journal February 2015
Natural triple excitations in local coupled cluster calculations with pair natural orbitals journal October 2013
Excited States of Butadiene to Chemical Accuracy: Reconciling Theory and Experiment journal September 2012
Communication: Automatic code generation enables nuclear gradient computations for fully internally contracted multireference theory journal February 2015
Third-order multireference perturbation theory: The n-electron valence state perturbation-theory approach journal February 2006
A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions journal May 1989
The Ground State Potential for the Chromium Dimer Revisited journal January 2003
Reactivity of the Binuclear Non-Heme Iron Active Site of Δ 9 Desaturase Studied by Large-Scale Multireference Ab Initio Calculations journal October 2014
Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics journal August 2014
The Cr2 potential energy curve studied with multiconfigurational second-order perturbation theory journal December 1994
n -electron valence state perturbation theory: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants journal November 2002
A time-dependent formulation of multi-reference perturbation theory journal February 2016
A new singlet-excited state of all-trans-spheroidene as detected by resonance-Raman excitation profiles journal January 1999
Ideas of relativistic quantum chemistry journal July 2010
Density Relaxation in Time-Dependent Density Functional Theory: Combining Relaxed Density Natural Orbitals and Multireference Perturbation Theories for an Improved Description of Excited States journal July 2014
An efficient and near linear scaling pair natural orbital based local coupled cluster method journal January 2013
Multireference Møller—Plesset method journal March 1992
Theory of the Electronic Spectra and Structure of the Polyacenes and of Alternant Hydrocarbons journal February 1956
Orbital optimization in the density matrix renormalization group, with applications to polyenes and β-carotene journal April 2008
Exact decoupling of the relativistic Fock operator journal January 2012
Exact decoupling of the relativistic Fock operator text January 2012
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988
A driven similarity renormalization group approach to quantum many-body problems text January 2014
The density matrix renormalization group for ab initio quantum chemistry text January 2014
A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry text January 2014
A time-dependent formulation of multi-reference perturbation theory text January 2015
Matrix Product Operators, Matrix Product States, and ab initio Density Matrix Renormalization Group algorithms preprint January 2016
The density-matrix renormalization group text January 2004

Cited By (9)

Multireference Approaches to Spin‐State Energetics of Transition Metal Complexes Utilizing the Density Matrix Renormalization Group journal February 2019
Driven similarity renormalization group for excited states: A state-averaged perturbation theory journal March 2018
Reduced scaling CASPT2 using supporting subspaces and tensor hyper-contraction journal July 2018
Multi-reference algebraic diagrammatic construction theory for excited states: General formulation and first-order implementation journal November 2018
Downfolding of many-body Hamiltonians using active-space models: Extension of the sub-system embedding sub-algebras approach to unitary coupled cluster formalisms journal July 2019
Evaluation of full valence correlation energies and gradients journal June 2019
Multireference configuration interaction and perturbation theory without reduced density matrices journal December 2019
The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges journal January 2020
Multireference configuration interaction and perturbation theory without reduced density matrices text January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
polymers
correlation energy
transition metals
chemical elements
excitation energies
matrix product state
time dependent formulation
dissociation energy
perturbation theory
density matrix renormalization group