Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Accurate Isomerization Enthalpy and Investigation of the Errors in Density Functional Theory for Dihydroazulene/Vinylheptafulvene Photochromism Using Diffusion Monte Carlo

Abstract

In this paper, we investigate the isomerization enthalpy of the dihydroazulene/vinylheptafulvene (DHA/VHF) molecular photoswitch system derivatives using electronic structure calculation methods including density functional theory (DFT), quantum Monte Carlo (QMC), and coupled cluster (CCSD(T)). Recent efforts have focused on tuning the isomerization enthalpy of the photoswitch for solar thermal energy storage applications using substitutional functional groups on its five- and seven-membered carbon rings, predominantly using DFT for the energy predictions. However, using the higher accuracy QMC and CCSD(T) methods, we show that in many cases DFT incorrectly predicts the isomerization enthalpy, and the errors depend on the functional groups substituted and the choice of the DFT functional. Isomerization of the DHA to VHF molecule is an electrocyclic ring-opening reaction on the five-membered ring of the DHA isomer. We find that the DFT errors are correlated to the electrocyclic ring-opening reactions of cyclobutene and cyclo-1,3-hexadiene, such that the DFT error changes monotonically with the size of the carbon ring, although QMC and CCSD(T) results are in a good agreement irrespective of the ring size. Using the QMC and CCSD(T) isomerization enthalpies, we predict gravimetric energy densities of the DHA derivatives for solar thermal storage applications. Our results show that suitable substitutionsmore » on DHA can yield gravimetric storage densities as large as 732 kJ/kg.« less

Authors:
ORCiD logo [1];  [1]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1483646
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 48; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Saritas, Kayahan, and Grossman, Jeffrey C. Accurate Isomerization Enthalpy and Investigation of the Errors in Density Functional Theory for Dihydroazulene/Vinylheptafulvene Photochromism Using Diffusion Monte Carlo. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b09437.
Copy to clipboard
Saritas, Kayahan, & Grossman, Jeffrey C. Accurate Isomerization Enthalpy and Investigation of the Errors in Density Functional Theory for Dihydroazulene/Vinylheptafulvene Photochromism Using Diffusion Monte Carlo. United States. https://doi.org/10.1021/acs.jpcc.7b09437
Copy to clipboard
Saritas, Kayahan, and Grossman, Jeffrey C. Wed . "Accurate Isomerization Enthalpy and Investigation of the Errors in Density Functional Theory for Dihydroazulene/Vinylheptafulvene Photochromism Using Diffusion Monte Carlo". United States. https://doi.org/10.1021/acs.jpcc.7b09437. https://www.osti.gov/servlets/purl/1483646.
Copy to clipboard
@article{osti_1483646,
title = {Accurate Isomerization Enthalpy and Investigation of the Errors in Density Functional Theory for Dihydroazulene/Vinylheptafulvene Photochromism Using Diffusion Monte Carlo},
author = {Saritas, Kayahan and Grossman, Jeffrey C.},
abstractNote = {In this paper, we investigate the isomerization enthalpy of the dihydroazulene/vinylheptafulvene (DHA/VHF) molecular photoswitch system derivatives using electronic structure calculation methods including density functional theory (DFT), quantum Monte Carlo (QMC), and coupled cluster (CCSD(T)). Recent efforts have focused on tuning the isomerization enthalpy of the photoswitch for solar thermal energy storage applications using substitutional functional groups on its five- and seven-membered carbon rings, predominantly using DFT for the energy predictions. However, using the higher accuracy QMC and CCSD(T) methods, we show that in many cases DFT incorrectly predicts the isomerization enthalpy, and the errors depend on the functional groups substituted and the choice of the DFT functional. Isomerization of the DHA to VHF molecule is an electrocyclic ring-opening reaction on the five-membered ring of the DHA isomer. We find that the DFT errors are correlated to the electrocyclic ring-opening reactions of cyclobutene and cyclo-1,3-hexadiene, such that the DFT error changes monotonically with the size of the carbon ring, although QMC and CCSD(T) results are in a good agreement irrespective of the ring size. Using the QMC and CCSD(T) isomerization enthalpies, we predict gravimetric energy densities of the DHA derivatives for solar thermal storage applications. Our results show that suitable substitutions on DHA can yield gravimetric storage densities as large as 732 kJ/kg.},
doi = {10.1021/acs.jpcc.7b09437},
journal = {Journal of Physical Chemistry. C},
number = 48,
volume = 121,
place = {United States},
year = {Wed Nov 08 00:00:00 EST 2017},
month = {Wed Nov 08 00:00:00 EST 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b09437
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Ground state potential energy surface for the DHA/VHF photoswitch system. Ground state, metastable state and transition state structures are enumerated from 1a to 1e. $Δ$H1 is the energy difference between the ground state and lowest energy metastable state, DHA and s-trans-VHF. $Δ$E$_a$ is the back reaction activation barrier.
All figures and tables (7 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Diarylethenes for Memories and Switches
journal, May 2000

Making molecular machines work
journal, October 2006

Fulgides for Memories and Switches
journal, March 2000

Chemical solutions for the closed-cycle storage of solar energy
journal, January 2011

  • Kucharski, Timothy J.; Tian, Yancong; Akbulatov, Sergey
  • Energy & Environmental Science, Vol. 4, Issue 11
  • DOI: 10.1039/c1ee01861b

Templated assembly of photoswitches significantly increases the energy-storage capacity of solar thermal fuels
journal, April 2014

  • Kucharski, Timothy J.; Ferralis, Nicola; Kolpak, Alexie M.
  • Nature Chemistry, Vol. 6, Issue 5
  • DOI: 10.1038/nchem.1918

Azobenzene-Functionalized Carbon Nanotubes As High-Energy Density Solar Thermal Fuels
journal, August 2011

  • Kolpak, Alexie M.; Grossman, Jeffrey C.
  • Nano Letters, Vol. 11, Issue 8
  • DOI: 10.1021/nl201357n

Conformal Electroplating of Azobenzene-Based Solar Thermal Fuels onto Large-Area and Fiber Geometries
journal, September 2016

  • Zhitomirsky, David; Grossman, Jeffrey C.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 39
  • DOI: 10.1021/acsami.6b08034

Molecularly Engineered Azobenzene Derivatives for High Energy Density Solid-State Solar Thermal Fuels
journal, March 2017

  • Cho, Eugene N.; Zhitomirsky, David; Han, Grace G. D.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 10
  • DOI: 10.1021/acsami.6b15018

Designing photoswitches for molecular solar thermal energy storage
journal, March 2015

Comparative Ab-Initio Study of Substituted Norbornadiene-Quadricyclane Compounds for Solar Thermal Storage
journal, February 2016

  • Kuisma, Mikael J.; Lundin, Angelica M.; Moth-Poulsen, Kasper
  • The Journal of Physical Chemistry C, Vol. 120, Issue 7
  • DOI: 10.1021/acs.jpcc.5b11489

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar-Thermal Energy Storage
journal, August 2016

  • Quant, Maria; Lennartson, Anders; Dreos, Ambra
  • Chemistry - A European Journal, Vol. 22, Issue 37
  • DOI: 10.1002/chem.201602530

Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity
journal, December 2016

  • Hansen, Mia Harring; Elm, Jonas; Olsen, Stine T.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 49
  • DOI: 10.1021/acs.jpca.6b09646

Dihydroazulene: from controlling photochromism to molecular electronics devices
journal, January 2014

  • Broman, Søren Lindbæk; Nielsen, Mogens Brøndsted
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 39
  • DOI: 10.1039/C4CP02442G

Dihydroazulene/vinylheptafulvene photochromism: effects of substituents, solvent, and temperature in the photorearrangement of dihydroazulenes to vinylheptafulvenes
journal, April 1993

  • Goerner, Helmut; Fischer, Christian; Gierisch, Sebastian
  • The Journal of Physical Chemistry, Vol. 97, Issue 16
  • DOI: 10.1021/j100118a030

Dihydroazulene/Vinylheptafulvene Photochromism:  A Model for One-Way Photochemistry via a Conical Intersection
journal, February 2002

  • Boggio-Pasqua, Martial; Bearpark, Michael J.; Hunt, Patricia A.
  • Journal of the American Chemical Society, Vol. 124, Issue 7
  • DOI: 10.1021/ja0161655

On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion
journal, March 1982

  • Rau, Hermann; Lueddecke, Erik
  • Journal of the American Chemical Society, Vol. 104, Issue 6
  • DOI: 10.1021/ja00370a028

Photoisomerization Quantum Yield of Azobenzene-Modified DNA Depends on Local Sequence
journal, May 2013

  • Yan, Yunqi; Wang, Xin; Chen, Jennifer I. L.
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja403249u

Photoreaction of Matrix-Isolated Dihydroazulene-Functionalized Molecules on Au{111}
journal, January 2013

  • Pathem, Bala Krishna; Zheng, Yue Bing; Morton, Seth
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl304102n

Arylethynyl Derivatives of the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch: Tuning the Switching Event
journal, June 2010

  • Broman, Søren Lindbæk; Petersen, Michael Åxman; Tortzen, Christian G.
  • Journal of the American Chemical Society, Vol. 132, Issue 26
  • DOI: 10.1021/ja103235g

A Bis(heptafulvenyl)-dicyanoethylene Thermoswitch with Two Sites for Ring Closure
journal, December 2011

  • Broman, Søren Lindbæk; Petersen, Anne Ugleholdt; Tortzen, Christian Gregers
  • Organic Letters, Vol. 14, Issue 1
  • DOI: 10.1021/ol2030586

On the Condensed Phase Ring-Closure of Vinylheptafulvalene and Ring-Opening of Gaseous Dihydroazulene
journal, April 2013

  • Schalk, Oliver; Broman, Søren L.; Petersen, Michael Å.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 16
  • DOI: 10.1021/jp400616c

Characterisation of dihydroazulene and vinylheptafulvene derivatives using Raman spectroscopy: The CN-stretching region
journal, May 2016

  • Hansen, Anne S.; Mackeprang, Kasper; Broman, Søren L.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 161
  • DOI: 10.1016/j.saa.2016.02.017

Computational Methodology Study of the Optical and Thermochemical Properties of a Molecular Photoswitch
journal, January 2015

  • Olsen, Stine T.; Elm, Jonas; Storm, Freja Eilsø
  • The Journal of Physical Chemistry A, Vol. 119, Issue 5
  • DOI: 10.1021/jp510678u

Towards Solar Energy Storage in the Photochromic Dihydroazulene-Vinylheptafulvene System
journal, April 2015

  • Cacciarini, Martina; Skov, Anders B.; Jevric, Martyn
  • Chemistry - A European Journal, Vol. 21, Issue 20
  • DOI: 10.1002/chem.201500100

Substituents effect on thermal electrocyclic reaction of dihydroazulene–vinylheptafulvene photoswitch: a DFT study to improve the photoswitch
journal, February 2013

Photosensitive Dihydroazulenes with Chromogenic Properties
journal, December 1984

  • Daub, Jörg; Knöchel, Thomas; Mannschreck, Albrecht
  • Angewandte Chemie International Edition in English, Vol. 23, Issue 12
  • DOI: 10.1002/anie.198409601

Inhomogeneous Electron Gas
journal, November 1964

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Ground State of the Electron Gas by a Stochastic Method
journal, August 1980

Quantum Monte Carlo simulations of solids
journal, January 2001

A direct coupled cluster algorithm for massively parallel computers
journal, January 1997

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

Using redundant internal coordinates to optimize equilibrium geometries and transition states
journal, January 1996

Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Reaction pathways by quantum Monte Carlo: Insight on the torsion barrier of 1,3-butadiene, and the conrotatory ring opening of cyclobutene
journal, December 2012

  • Barborini, Matteo; Guidoni, Leonardo
  • The Journal of Chemical Physics, Vol. 137, Issue 22
  • DOI: 10.1063/1.4769791

Jastrow correlation factor for atoms, molecules, and solids
journal, December 2004

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

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

Size-consistent variational approaches to nonlocal pseudopotentials: Standard and lattice regularized diffusion Monte Carlo methods revisited
journal, April 2010

  • Casula, Michele; Moroni, Saverio; Sorella, Sandro
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3380831

Biosynthetic and Biomimetic Electrocyclizations
journal, December 2005

  • Beaudry, Christopher M.; Malerich, Jeremiah P.; Trauner, Dirk
  • Chemical Reviews, Vol. 105, Issue 12
  • DOI: 10.1021/cr0406110

Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003

  • Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin
  • The Journal of Chemical Physics, Vol. 119, Issue 23
  • DOI: 10.1063/1.1626543

Understanding and Reducing Errors in Density Functional Calculations
journal, August 2013

Challenges for Density Functional Theory
journal, December 2011

  • Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200107z

Density functional theory is straying from the path toward the exact functional
journal, January 2017

  • Medvedev, Michael G.; Bushmarinov, Ivan S.; Sun, Jianwei
  • Science, Vol. 355, Issue 6320
  • DOI: 10.1126/science.aah5975

Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
journal, September 2003

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Recent progress in the development of molecular-scale electronics based on photoswitchable molecules
    journal, January 2020

    • Huang, Xianhui; Li, Tao
    • Journal of Materials Chemistry C, Vol. 8, Issue 3
    • DOI: 10.1039/c9tc06054e
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 4)figure
      Figure 2 (p. 5)figure
      Figure 3 (p. 8)figure
      Figure 4 (p. 8)figure
      Figure 5 (p. 9)figure
      Figure 6 (p. 11)figure
      Figure 7 (p. 12)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: