Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5088120· OSTI ID:1612369
 [1];  [2];  [3]
  1. Emory Univ., Atlanta, GA (United States); DOE/OSTI
  2. Uppsala Univ. (Sweden)
  3. Emory Univ., Atlanta, GA (United States)
+ Show Author Affiliations
In this paper, we introduce two new approaches to compute near-degenerate electronic states based on the driven similarity renormalization group (DSRG) framework. The first approach is a unitary multi-state formalism based on the DSRG (MS-DSRG), whereby an effective Hamiltonian is built from a set of state-specific solutions. The second approach employs a dynamic weighting parameter to smoothly interpolate between the multi-state and the state-averaged DSRG schemes. The resulting dynamically weighted DSRG (DW-DSRG) theory incorporates the most desirable features of both multi-state approaches (ability to accurately treat many states) and state-averaged methods (correct description of avoided crossings and conical intersections). We formulate second-order perturbation theories (PT2) based on the MS- and DW-DSRG and study the potential energy curves of LiF, the conical intersection of the two lowest singlet states of NH3, and several low-lying excited states of benzene, naphthalene, and anthracene. The DW-DSRG-PT2 predicts the correct avoided crossing of LiF and avoids artifacts produced by the corresponding state-specific and multi-state theories. Excitation energies of the acenes computed with the DW-DSRG-PT2 are found to be more accurate than the corresponding state-averaged values, showing a small dependence on the number of states computed.
Research Organization:
Emory Univ., Atlanta, GA (United States)
Sponsoring Organization:
Alfred P. Sloan Foundation; National Science Foundation (NSF); Swedish Research Council (VR); USDOE Office of Science (SC); Wenner-Gren Foundation
Grant/Contract Number:
SC0016004
OSTI ID:
1612369
Alternate ID(s):
OSTI ID: 1505880
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 150; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (51)

Hartree–Fock exchange fitting basis sets for H to Rn journal January 2007
Multiconfigurational second-order perturbative methods: Overview and comparison of basic properties journal January 1995
Improved direct diabatization and coupled potential energy surfaces for the photodissociation of ammonia journal March 2007
Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg journal May 2010
SDS: the ‘static–dynamic–static’ framework for strongly correlated electrons journal April 2014
Multiconfigurational second-order perturbative methods: Overview and comparison of basic properties journal January 1995
Theoretical study of the valence π → π * excited states of polyacenes: anthracene and naphthacene
  • Kawashima, Yukio; Hashimoto, Tomohiro; Nakano, Haruyuki
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 102, Issue 1-6 https://doi.org/10.1007/s002140050472
journal June 1999
Generalized antisymmetric ordered products, generalized normal ordered products, ordered and ordinary cumulants and their use in many electron correlation problem journal January 2013
Normal ordering and a Wick-like reduction theorem for fermions with respect to a multi-determinantal reference state journal August 1997
The multi-state CASPT2 method journal May 1998
Development of a size-consistent state-specific multireference perturbation theory with relaxed model-space coefficients journal January 1999
Multireference Driven Similarity Renormalization Group: A Second-Order Perturbative Analysis journal April 2015
Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States journal September 2017
Polarizable Embedding for Excited-State Reactions: Dynamically Weighted Polarizable QM/MM journal March 2018
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 journal January 2005
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
On the perturbation of multiconfiguration wave functions journal July 2003
Dynamically weighted multiconfiguration self-consistent field: Multistate calculations for F+H2O→HF+OH reaction paths journal April 2004
A quasidegenerate formulation of the second order n-electron valence state perturbation theory approach journal September 2004
Comparison of low-order multireference many-body perturbation theories journal April 2005
Direct calculation of coupled diabatic potential-energy surfaces for ammonia and mapping of a four-dimensional conical intersection seam journal March 2006
Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3 journal April 2008
Comparative study of multireference perturbative theories for ground and excited states journal November 2009
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory journal June 2011
Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients journal August 2011
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal October 1982
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Quasidegenerate perturbation theory with multiconfigurational self‐consistent‐field reference functions journal November 1993
Normal order and extended Wick theorem for a multiconfiguration reference wave function journal July 1997
A driven similarity renormalization group approach to quantum many-body problems journal August 2014
Communication: Smoothing out excited-state dynamics: Analytical gradients for dynamically weighted complete active space self-consistent field journal November 2014
Quasi-degenerate perturbation theory using matrix product states journal January 2016
Internally contracted multireference coupled-cluster theory in a multistate framework journal February 2016
Towards numerically robust multireference theories: The driven similarity renormalization group truncated to one- and two-body operators journal April 2016
An integral-factorized implementation of the driven similarity renormalization group second-order multireference perturbation theory journal May 2016
Driven similarity renormalization group: Third-order multireference perturbation theory journal March 2017
Driven similarity renormalization group for excited states: A state-averaged perturbation theory journal March 2018
Erratum: “Towards numerically robust multireference theories: The driven similarity renormalization group truncated to one- and two-body operators” [J. Chem. Phys. 144, 164114 (2016)] journal February 2018
Erratum: “Driven similarity renormalization group: Third-order multireference perturbation theory” [J. Chem. Phys. 146, 124132 (2017)] journal February 2018
Further development of SDSPT2 for strongly correlated electrons journal January 2017
Coupled-cluster method for multideterminantal reference states journal October 1981
Qualitative intruder-state problems in effective Hamiltonian theory and their solution through intermediate Hamiltonians journal June 1987
Application of Hilbert-space coupled-cluster theory to simple ( H 2 ) 2 model systems: Planar models journal April 1993
Complete set of solutions of multireference coupled-cluster equations: The state-universal formalism journal April 2000
Coupled-cluster theory in quantum chemistry journal February 2007
An Antifungal Polycyclic Tetramate Macrolactam, Heat-Stable Antifungal Factor (HSAF), Is a Novel Oxidative Stress Modulator in Lysobacter enzymogenes journal April 2021
A driven similarity renormalization group approach to quantum many-body problems text January 2014
An integral-factorized implementation of the driven similarity renormalization group second-order multireference perturbation theory text January 2016
Deazaflavin reductive photocatalysis involves excited semiquinone radicals text January 2020
Further development of SDSPT2 for strongly correlated electrons text January 2017
Further development of SDSPT2 for strongly correlated electrons text January 2017

Cited By (2)

Extended Dynamically Weighted CASPT2: The Best of Two Worlds journal February 2020
The combination of multipartitioning of the Hamiltonian with canonical Van Vleck perturbation theory leads to a Hermitian variant of quasidegenerate N-electron valence perturbation theory journal January 2020

Similar Records

Driven similarity renormalization group for excited states: A state-averaged perturbation theory
Journal Article · Thu Mar 22 20:00:00 EDT 2018 · Journal of Chemical Physics · OSTI ID:1511175

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Degenerate energy levels
Density-matrix
Excitation energies
Perturbation theory
Physics
Potential energy surfaces
Renormalization and regularization