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Title: A time-dependent formulation of multi-reference perturbation theory

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4941606· OSTI ID:1469673
 [1];  [1]
  1. Princeton Univ., Princeton, NJ (United States)
+ Show Author Affiliations

Here, we discuss the time-dependent formulation of perturbation theory in the context of the interacting zeroth-order Hamiltonians that appear in multi-reference situations. As an example, we present a time-dependent formulation and implementation of second-order n-electron valence perturbation theory. The resulting time-dependent n-electron valence second-order perturbation theory (t-NEVPT2) method yields the fully uncontracted n-electron valence perturbation wavefunction and energy, but has a lower computational scaling than the usual contracted variants, and also avoids the construction of high-order density matrices and the diagonalization of metrics.We present results of t-NEVPT2 for the water, nitrogen, carbon, and chromium molecules and outline directions for the future.

Research Organization:
Princeton Univ., NJ (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0008624; SC0010530
OSTI ID:
1469673
Alternate ID(s):
OSTI ID: 1237776
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

References (61)

Complete vs Restricted Active Space Perturbation Theory Calculation of the Cr 2 Potential Energy Surface journal April 2011
Continuous transition between Brillouin–Wigner and Rayleigh–Schrödinger perturbation theory, generalized Bloch equation, and Hilbert space multireference coupled cluster journal June 2003
Communication: A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states journal September 2014
Size-consistency corrections for configuration interaction calculations journal May 1988
Multiconfigurational perturbation theory with level shift — the Cr2 potential revisited journal October 1995
Consistent generalization of the Møller-Plesset partitioning to open-shell and multiconfigurational SCF reference states in many-body perturbation theory journal October 1987
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
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
A coupled-cluster approach to the many-body perturbation theory for open-shell systems journal March 1978
Complete set of solutions of the generalized Bloch equation journal January 2000
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
Applications of a non-perturbative many-body formalism to general open-shell atomic and molecular problems: calculation of the ground and the lowest π-π* singlet and triplet energies and the first ionization potential of trans-butadiene journal April 1977
Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces journal August 1988
N-electron valence state perturbation theory: a fast implementation of the strongly contracted variant journal December 2001
Second‐order perturbation theory with a complete active space self‐consistent field reference function journal January 1992
Introduction of n -electron valence states for multireference perturbation theory journal June 2001
The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water journal May 1993
Ab initio quantum chemistry using the density matrix renormalization group journal March 1999
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
Laplace transform techniques in Mo/ller–Plesset perturbation theory journal January 1992
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
High-performance ab initio density matrix renormalization group method: Applicability to large-scale multireference problems for metal compounds journal June 2009
Configuration interaction calculations on the nitrogen molecule journal January 1974
Generalizations of the direct CI method based on the graphical unitary group approach. II. Single and double replacements from any set of reference configurations journal February 1980
The Cr2 potential curve: a multireference pair functional treatment journal June 1996
Canonical transformation theory from extended normal ordering journal September 2007
The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations book January 1987
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
Communication: Multireference equation of motion coupled cluster: A transform and diagonalize approach to electronic structure journal February 2014
A driven similarity renormalization group approach to quantum many-body problems journal August 2014
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
A state-specific multi-reference coupled cluster formalism with molecular applications journal May 1998
Normal order and extended Wick theorem for a multiconfiguration reference wave function journal July 1997
Multireference Driven Similarity Renormalization Group: A Second-Order Perturbative Analysis journal April 2015
An orbital-invariant internally contracted multireference coupled cluster approach journal March 2011
CheMPS2: A free open-source spin-adapted implementation of the density matrix renormalization group for ab initio quantum chemistry journal June 2014
Canonical transformation theory for multireference problems journal May 2006
A size-consistent state-specific multireference coupled cluster theory: Formal developments and molecular applications journal April 1999
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
Coupling term derivation and general implementation of state-specific multireference coupled cluster theories journal July 2007
Third-order multireference perturbation theory: The n-electron valence state perturbation-theory approach journal February 2006
Communication: The description of strong correlation within self-consistent Green's function second-order perturbation theory journal June 2014
The Ground State Potential for the Chromium Dimer Revisited journal January 2003
Communication: Towards ab initio self-energy embedding theory in quantum chemistry journal December 2015
The restricted active space self-consistent-field method, implemented with a split graph unitary group approach journal July 1990
A transformed framework for dynamic correlation in multireference problems journal March 2015
The Cr2 potential energy curve studied with multiconfigurational second-order perturbation theory journal December 1994
Elimination of energy denominators in Møller—Plesset perturbation theory by a Laplace transform approach journal June 1991
Basis-set convergence of correlated calculations on water journal June 1997
Third-order multireference perturbation theory The CASPT3 method journal October 1996
Multireference linearized coupled cluster theory for strongly correlated systems using matrix product states journal September 2015

Cited By (13)

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 text January 2017
The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges journal January 2020
Driven similarity renormalization group: Third-order multireference perturbation theory journal March 2017
A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions journal May 2016
Exact and approximate adiabatic connection formulae for the correlation energy in multireference ground and excited states journal November 2018
CASSCF linear response calculations for large open-shell molecules journal May 2019
Reduced scaling CASPT2 using supporting subspaces and tensor hyper-contraction journal July 2018
Chemically accurate excitation energies with small basis sets journal October 2019
Multi-reference algebraic diagrammatic construction theory for excited states: General formulation and first-order implementation journal November 2018
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 June 2017
Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group text January 2016
Efficient and Stochastic Multireference Perturbation Theory for Large Active Spaces within a Full Configuration Interaction Quantum Monte Carlo Framework text January 2019
Efficient and stochastic multireference perturbation theory for large active spaces within a full configuration interaction quantum Monte Carlo framework journal February 2020

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