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Title: Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo

Abstract

We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method, this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. As a result, we demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.

Authors:
 [1]; ORCiD logo [1]
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  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
Contributing Org.:
Lawrence Berkeley National Laboratory, University of California, Berkeley
OSTI Identifier:
1409183
Alternate Identifier(s):
OSTI ID: 1420662
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 19; Related Information: http://www.qmcpack.org; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Quantum Monte Carlo; Electronic structure theory; Charge transfer; Excited states; Electron correlation

Citation Formats

Blunt, Nick S., and Neuscamman, Eric. Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo. United States: N. p., 2017. Web. doi:10.1063/1.4998197.
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Blunt, Nick S., & Neuscamman, Eric. Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo. United States. https://doi.org/10.1063/1.4998197
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Blunt, Nick S., and Neuscamman, Eric. Thu . "Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo". United States. https://doi.org/10.1063/1.4998197. https://www.osti.gov/servlets/purl/1409183.
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@article{osti_1409183,
title = {Charge-transfer excited states: Seeking a balanced and efficient wave function ansatz in variational Monte Carlo},
author = {Blunt, Nick S. and Neuscamman, Eric},
abstractNote = {We present a simple and efficient wave function ansatz for the treatment of excited charge-transfer states in real-space quantum Monte Carlo methods. Using the recently-introduced variation-after-response method, this ansatz allows a crucial orbital optimization step to be performed beyond a configuration interaction singles expansion, while only requiring calculation of two Slater determinant objects. As a result, we demonstrate this ansatz for the illustrative example of the stretched LiF molecule, for a range of excited states of formaldehyde, and finally for the more challenging ethylene-tetrafluoroethylene molecule.},
doi = {10.1063/1.4998197},
journal = {Journal of Chemical Physics},
number = 19,
volume = 147,
place = {United States},
year = {Thu Nov 16 00:00:00 EST 2017},
month = {Thu Nov 16 00:00:00 EST 2017}
}
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https://doi.org/10.1063/1.4998197
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Works referenced in this record:

Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method
journal, March 2009

  • Neese, Frank; Wennmohs, Frank; Hansen, Andreas
  • The Journal of Chemical Physics, Vol. 130, Issue 11
  • DOI: 10.1063/1.3086717

Monte-Carlo solution of Schrödinger's equation
journal, February 1971

Equation of Motion Theory for Excited States in Variational Monte Carlo and the Jastrow Antisymmetric Geminal Power in Hilbert Space
journal, July 2016

  • Zhao, Luning; Neuscamman, Eric
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00480

Excited state calculations using phaseless auxiliary-field quantum Monte Carlo: Potential energy curves of low-lying C2 singlet states
journal, March 2009

  • Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry
  • The Journal of Chemical Physics, Vol. 130, Issue 9
  • DOI: 10.1063/1.3077920

Absorption Spectrum of the Green Fluorescent Protein Chromophore: A Difficult Case for ab Initio Methods?
journal, July 2009

  • Filippi, Claudia; Zaccheddu, Maurizio; Buda, Francesco
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 8
  • DOI: 10.1021/ct900227j

Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
journal, March 2013

  • Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr300503r

A diffusion Monte Carlo algorithm with very small time‐step errors
journal, August 1993

  • Umrigar, C. J.; Nightingale, M. P.; Runge, K. J.
  • The Journal of Chemical Physics, Vol. 99, Issue 4
  • DOI: 10.1063/1.465195

Optimized Jastrow–Slater wave functions for ground and excited states: Application to the lowest states of ethene
journal, June 2004

  • Schautz, Friedemann; Filippi, Claudia
  • The Journal of Chemical Physics, Vol. 120, Issue 23
  • DOI: 10.1063/1.1752881

Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene
journal, May 2013

An extension of the coupled cluster formalism to excited states (I)
journal, January 1981

Inhomogeneous backflow transformations in quantum Monte Carlo calculations
journal, December 2006

Communication: Excited states, dynamic correlation functions and spectral properties from full configuration interaction quantum Monte Carlo
journal, November 2012

  • Booth, George H.; Chan, Garnet Kin-Lic
  • The Journal of Chemical Physics, Vol. 137, Issue 19
  • DOI: 10.1063/1.4766327

Communication: Variation after response in quantum Monte Carlo
journal, August 2016

  • Neuscamman, Eric
  • The Journal of Chemical Physics, Vol. 145, Issue 8
  • DOI: 10.1063/1.4961686

Fast linear scaling second-order Møller-Plesset perturbation theory (MP2) using local and density fitting approximations
journal, May 2003

  • Werner, Hans-Joachim; Manby, Frederick R.; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564816

The calculation of excited state properties with quantum Monte Carlo
journal, November 1988

  • Ceperley, D. M.; Bernu, B.
  • The Journal of Chemical Physics, Vol. 89, Issue 10
  • DOI: 10.1063/1.455398

Energy-consistent pseudopotentials for quantum Monte Carlo calculations
journal, June 2007

  • Burkatzki, M.; Filippi, C.; Dolg, M.
  • The Journal of Chemical Physics, Vol. 126, Issue 23
  • DOI: 10.1063/1.2741534

Correlated geminal wave function for molecules: An efficient resonating valence bond approach
journal, October 2004

  • Casula, Michele; Attaccalite, Claudio; Sorella, Sandro
  • The Journal of Chemical Physics, Vol. 121, Issue 15
  • DOI: 10.1063/1.1794632

The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission
journal, April 2014

  • Zeng, Tao; Hoffmann, Roald; Ananth, Nandini
  • Journal of the American Chemical Society, Vol. 136, Issue 15
  • DOI: 10.1021/ja500887a

Coulombic potential energy integrals and approximations
journal, May 1973

  • Whitten, J. L.
  • The Journal of Chemical Physics, Vol. 58, Issue 10
  • DOI: 10.1063/1.1679012

Communication: Configuration interaction singles has a large systematic bias against charge-transfer states
journal, August 2011

  • Subotnik, Joseph E.
  • The Journal of Chemical Physics, Vol. 135, Issue 7
  • DOI: 10.1063/1.3627152

Linear-Scaling Quantum Monte Carlo Calculations
journal, November 2001

A Bayesian analysis of Green’s function Monte Carlo correlation functions
journal, December 1992

  • Caffarel, M.; Ceperley, D. M.
  • The Journal of Chemical Physics, Vol. 97, Issue 11
  • DOI: 10.1063/1.463411

The orbital-specific virtual local triples correction: OSV-L(T)
journal, February 2013

  • Schütz, Martin; Yang, Jun; Chan, Garnet Kin-Lic
  • The Journal of Chemical Physics, Vol. 138, Issue 5
  • DOI: 10.1063/1.4789415

Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3
journal, April 2008

  • Schreiber, Marko; Silva-Junior, Mario R.; Sauer, Stephan P. A.
  • The Journal of Chemical Physics, Vol. 128, Issue 13
  • DOI: 10.1063/1.2889385

Projector Quantum Monte Carlo Method for Nonlinear Wave Functions
journal, April 2017

Computing the energy of a water molecule using multideterminants: A simple, efficient algorithm
journal, December 2011

  • Clark, Bryan K.; Morales, Miguel A.; McMinis, Jeremy
  • The Journal of Chemical Physics, Vol. 135, Issue 24
  • DOI: 10.1063/1.3665391

Accuracy of electronic wave functions in quantum Monte Carlo: The effect of high-order correlations
journal, August 1997

  • Huang, Chien-Jung; Umrigar, C. J.; Nightingale, M. P.
  • The Journal of Chemical Physics, Vol. 107, Issue 8
  • DOI: 10.1063/1.474658

Photochemistry induced by metal-to-ligand charge transfer excitation
journal, October 2000

Optimizing the Energy with Quantum Monte Carlo: A Lower Numerical Scaling for Jastrow–Slater Expansions
journal, October 2017

  • Assaraf, Roland; Moroni, S.; Filippi, Claudia
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 11
  • DOI: 10.1021/acs.jctc.7b00648

Simple formalism for efficient derivatives and multi-determinant expansions in quantum Monte Carlo
journal, May 2016

  • Filippi, Claudia; Assaraf, Roland; Moroni, Saverio
  • The Journal of Chemical Physics, Vol. 144, Issue 19
  • DOI: 10.1063/1.4948778

Resonating valence bond wave function with molecular orbitals: Application to first-row molecules
journal, October 2009

  • Marchi, Mariapia; Azadi, Sam; Casula, Michele
  • The Journal of Chemical Physics, Vol. 131, Issue 15
  • DOI: 10.1063/1.3249966

Photoinduced charge transfer processes in solar photocatalysis based on modified TiO 2
journal, January 2016

  • Park, Hyunwoong; Kim, Hyoung-il; Moon, Gun-hee
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/c5ee02575c

Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules
journal, November 2005

  • Dreuw, Andreas; Head-Gordon, Martin
  • Chemical Reviews, Vol. 105, Issue 11
  • DOI: 10.1021/cr0505627

Chemiluminescence spectra from cool and blue flames: Electronically excited formaldehyde
journal, October 1973

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

A random‐walk simulation of the Schrödinger equation: H + 3
journal, August 1975

  • Anderson, James B.
  • The Journal of Chemical Physics, Vol. 63, Issue 4
  • DOI: 10.1063/1.431514

An excited-state approach within full configuration interaction quantum Monte Carlo
journal, October 2015

  • Blunt, N. S.; Smart, Simon D.; Booth, George H.
  • The Journal of Chemical Physics, Vol. 143, Issue 13
  • DOI: 10.1063/1.4932595

Communication: A Jastrow factor coupled cluster theory for weak and strong electron correlation
journal, November 2013

  • Neuscamman, Eric
  • The Journal of Chemical Physics, Vol. 139, Issue 18
  • DOI: 10.1063/1.4829536

Excitations in photoactive molecules from quantum Monte Carlo
journal, September 2004

  • Schautz, Friedemann; Buda, Francesco; Filippi, Claudia
  • The Journal of Chemical Physics, Vol. 121, Issue 12
  • DOI: 10.1063/1.1777212

A Blocked Linear Method for Optimizing Large Parameter Sets in Variational Monte Carlo
journal, May 2017

  • Zhao, Luning; Neuscamman, Eric
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 6
  • DOI: 10.1021/acs.jctc.7b00119

Suppressing Ionic Terms with Number-Counting Jastrow Factors in Real Space
journal, April 2017

  • Goetz, Brett Van Der; Neuscamman, Eric
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 5
  • DOI: 10.1021/acs.jctc.7b00158

An Efficient Variational Principle for the Direct Optimization of Excited States
journal, July 2016

  • Zhao, Luning; Neuscamman, Eric
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00508

A theoretical perspective on charge transfer in photocatalysis. The example of Ir-based systems
journal, December 2015

  • Bokarev, Sergey I.; Bokareva, Olga S.; Kühn, Oliver
  • Coordination Chemistry Reviews, Vol. 304-305
  • DOI: 10.1016/j.ccr.2014.12.016

Diffusion quantum Monte Carlo calculations of the excited states of silicon
journal, May 1998

The Quantum Coherent Mechanism for Singlet Fission: Experiment and Theory
journal, April 2013

  • Chan, Wai-Lun; Berkelbach, Timothy C.; Provorse, Makenzie R.
  • Accounts of Chemical Research, Vol. 46, Issue 6
  • DOI: 10.1021/ar300286s

Applications of quantum Monte Carlo methods in condensed systems
journal, January 2011

Optimized trial wave functions for quantum Monte Carlo calculations
journal, April 1988

Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange
journal, August 2003

  • Dreuw, Andreas; Weisman, Jennifer L.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 119, Issue 6
  • DOI: 10.1063/1.1590951

Ab initio electronic structure of anions
journal, June 1987

  • Simons, Jack.; Jordan, Kenneth D.
  • Chemical Reviews, Vol. 87, Issue 3
  • DOI: 10.1021/cr00079a004

A doubles correction to electronic excited states from configuration interaction in the space of single substitutions
journal, March 1994

The Charge Transfer Problem in Density Functional Theory Calculations of Aqueously Solvated Molecules
journal, October 2013

  • Isborn, Christine M.; Mar, Brendan D.; Curchod, Basile F. E.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 40
  • DOI: 10.1021/jp4058274

Continuum variational and diffusion quantum Monte Carlo calculations
journal, December 2009

Improved Scaling for Quantum Monte Carlo on Insulators
journal, January 2011

  • Ahuja, Kapil; Clark, Bryan K.; de Sturler, Eric
  • SIAM Journal on Scientific Computing, Vol. 33, Issue 4
  • DOI: 10.1137/100805467

Communication: Adjusting charge transfer state energies for configuration interaction singles: Without any parameterization and with minimal cost
journal, April 2012

  • Liu, Xinle; Fatehi, Shervin; Shao, Yihan
  • The Journal of Chemical Physics, Vol. 136, Issue 16
  • DOI: 10.1063/1.4705757
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