DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations

Abstract

Density functional approximations (DFAs) are known to significantly overestimate the polarizabilities of long chain-like molecules. We study the static electric dipole polarizabilities and the vertical ionization potentials of polyacenes from benzene to pentacene using the Fermi–Löwdin orbital-based self-interaction corrected (FLOSIC) density functional method. The orbital by orbital self-interaction correction corrects for the overestimation tendency of DFAs. The polarizabilities calculated with FLOSIC-DFA are, however, overly corrected. We also tested the recently developed locally scaled self-interaction correction (LSIC) method on polyacenes. The local-scaling method applies full SIC in the one-electron regions and restores the proper behavior of the SIC exchange–correlation functionals in the uniform density limit. The results show that LSIC removes the overcorrection tendency of the FLOSIC-DFA and produces results that are in excellent agreement with reference coupled-cluster single and double values. The vertical ionization potentials with LSIC also show good agreement with available experimental values.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Texas at El Paso, TX (United States)
Publication Date:
Research Org.:
Univ. of Texas at El Paso, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1767138
Alternate Identifier(s):
OSTI ID: 1771813
Grant/Contract Number:  
SC0018331; SC0002168
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 154; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Akter, Sharmin, Yamamoto, Yoh, Zope, Rajendra R., and Baruah, Tunna. Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations. United States: N. p., 2021. Web. doi:10.1063/5.0041265.
Akter, Sharmin, Yamamoto, Yoh, Zope, Rajendra R., & Baruah, Tunna. Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations. United States. https://doi.org/10.1063/5.0041265
Akter, Sharmin, Yamamoto, Yoh, Zope, Rajendra R., and Baruah, Tunna. Fri . "Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations". United States. https://doi.org/10.1063/5.0041265. https://www.osti.gov/servlets/purl/1767138.
@article{osti_1767138,
title = {Static dipole polarizabilities of polyacenes using self-interaction-corrected density functional approximations},
author = {Akter, Sharmin and Yamamoto, Yoh and Zope, Rajendra R. and Baruah, Tunna},
abstractNote = {Density functional approximations (DFAs) are known to significantly overestimate the polarizabilities of long chain-like molecules. We study the static electric dipole polarizabilities and the vertical ionization potentials of polyacenes from benzene to pentacene using the Fermi–Löwdin orbital-based self-interaction corrected (FLOSIC) density functional method. The orbital by orbital self-interaction correction corrects for the overestimation tendency of DFAs. The polarizabilities calculated with FLOSIC-DFA are, however, overly corrected. We also tested the recently developed locally scaled self-interaction correction (LSIC) method on polyacenes. The local-scaling method applies full SIC in the one-electron regions and restores the proper behavior of the SIC exchange–correlation functionals in the uniform density limit. The results show that LSIC removes the overcorrection tendency of the FLOSIC-DFA and produces results that are in excellent agreement with reference coupled-cluster single and double values. The vertical ionization potentials with LSIC also show good agreement with available experimental values.},
doi = {10.1063/5.0041265},
journal = {Journal of Chemical Physics},
number = 11,
volume = 154,
place = {United States},
year = {Fri Mar 19 00:00:00 EDT 2021},
month = {Fri Mar 19 00:00:00 EDT 2021}
}

Works referenced in this record:

Electronic responses of long chains to electrostatic fields: Hartree-Fock vs. density-functional theory: A model study
journal, February 2014

  • Vargas, Jorge; Springborg, Michael; Kirtman, Bernard
  • The Journal of Chemical Physics, Vol. 140, Issue 5
  • DOI: 10.1063/1.4864038

Exchange-Correlation Hole in Polarized Insulators: Implications for the Microscopic Functional Theory of Dielectrics
journal, January 1998


Measurement of static polarizabilities on C 1 0 H 8 and C 1 0 D 8
journal, January 1992

  • Heitz, S.; Weidauer, D.; Rosenow, B.
  • The Journal of Chemical Physics, Vol. 96, Issue 2
  • DOI: 10.1063/1.462118

Charge redistribution and electronic polarization in organic molecular crystals
journal, July 2001


Localized orbitals and the Fermi hole
journal, January 1982

  • Luken, William L.; Beratan, David N.
  • Theoretica Chimica Acta, Vol. 61, Issue 3
  • DOI: 10.1007/bf00550971

Polarizabilities of π-Conjugated Chains Revisited: Improved Results from Broken-Symmetry Range-Separated DFT and New CCSD(T) Benchmarks
journal, July 2016

  • Oviedo, M. Belén; Ilawe, Niranjan V.; Wong, Bryan M.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00360

Local self-interaction correction method with a simple scaling factor
journal, January 2021

  • Romero, Selim; Yamamoto, Yoh; Baruah, Tunna
  • Physical Chemistry Chemical Physics, Vol. 23, Issue 3
  • DOI: 10.1039/d0cp06282k

Full self-consistency in the Fermi-orbital self-interaction correction
journal, May 2017


Benchmark theoretical study of the electric polarizabilities of naphthalene, anthracene, and tetracene
journal, January 2013

  • Huzak, M.; Deleuze, M. S.
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773018

Assessment of conventional density functional schemes for computing the polarizabilities and hyperpolarizabilities of conjugated oligomers: An ab initio investigation of polyacetylene chains
journal, December 1998

  • Champagne, Benoı̂t; Perpète, Eric A.; van Gisbergen, Stan J. A.
  • The Journal of Chemical Physics, Vol. 109, Issue 23
  • DOI: 10.1063/1.477731

Jacob’s ladder of density functional approximations for the exchange-correlation energy
conference, January 2001

  • Perdew, John P.
  • Density functional theory and its application to materials, AIP Conference Proceedings
  • DOI: 10.1063/1.1390175

Ab Initio Studies of Properties of Small Potassium Clusters
journal, December 2008

  • Banerjee, Arup; Ghanty, Tapan K.; Chakrabarti, Aparna
  • The Journal of Physical Chemistry A, Vol. 112, Issue 48
  • DOI: 10.1021/jp807571a

Static and Dynamic Polarizabilities of Conjugated Molecules and Their Cations
journal, December 2004

  • Smith, Stanley M.; Markevitch, Alexei N.; Romanov, Dmitri A.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 50
  • DOI: 10.1021/jp048864k

Experimental static dipole–dipole polarizabilities of molecules
journal, December 2013


Ab initio and density functional theory calculations of the dipole polarizabilities of ethene, benzene and naphthalene
journal, January 1998


High-resolution laser spectroscopy on the S1←S0 transition of jet-cooled anthracene: Rotational structure and Stark effect
journal, December 2007

  • Bendkowsky, Vera; Heinecke, Elke; Hese, Achim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2806184

Calculation of macroscopic linear and nonlinear optical susceptibilities for the naphthalene, anthracene and meta-nitroaniline crystals
journal, November 2000


Dynamic polarizabilities of polyaromatic hydrocarbons using coupled-cluster linear response theory
journal, October 2007

  • Hammond, Jeff R.; Kowalski, Karol; deJong, Wibe A.
  • The Journal of Chemical Physics, Vol. 127, Issue 14
  • DOI: 10.1063/1.2772853

Quantum theory of cohesive properties of solids
journal, January 1956


Untersuchungen zur molaren K err -Konstante
journal, February 1969


Perdew-Zunger self-interaction correction: How wrong for uniform densities and large- Z atoms?
journal, May 2019

  • Santra, Biswajit; Perdew, John P.
  • The Journal of Chemical Physics, Vol. 150, Issue 17
  • DOI: 10.1063/1.5090534

Accurate polymer polarizabilities with exact exchange density-functional theory
journal, December 2003

  • Mori-Sánchez, Paula; Wu, Qin; Yang, Weitao
  • The Journal of Chemical Physics, Vol. 119, Issue 21
  • DOI: 10.1063/1.1630011

Polyacenes electronic properties and their dependence on molecular size
journal, August 2008


Molecular calculations of excitation energies and (hyper)polarizabilities with a statistical average of orbital model exchange-correlation potentials
journal, January 2000

  • Schipper, P. R. T.; Gritsenko, O. V.; van Gisbergen, S. J. A.
  • The Journal of Chemical Physics, Vol. 112, Issue 3
  • DOI: 10.1063/1.480688

A step in the direction of resolving the paradox of Perdew–Zunger self-interaction correction. II. Gauge consistency of the energy density at three levels of approximation
journal, June 2020

  • Bhattarai, Puskar; Wagle, Kamal; Shahi, Chandra
  • The Journal of Chemical Physics, Vol. 152, Issue 21
  • DOI: 10.1063/5.0010375

A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction
journal, December 2019

  • Zope, Rajendra R.; Yamamoto, Yoh; Diaz, Carlos M.
  • The Journal of Chemical Physics, Vol. 151, Issue 21
  • DOI: 10.1063/1.5129533

Scaling down the Perdew-Zunger self-interaction correction in many-electron regions
journal, March 2006

  • Vydrov, Oleg A.; Scuseria, Gustavo E.; Perdew, John P.
  • The Journal of Chemical Physics, Vol. 124, Issue 9
  • DOI: 10.1063/1.2176608

Self-interaction corrections applied to Mg-porphyrin, C 60 , and pentacene molecules
journal, April 2016

  • Pederson, Mark R.; Baruah, Tunna; Kao, Der-you
  • The Journal of Chemical Physics, Vol. 144, Issue 16
  • DOI: 10.1063/1.4947042

The NIST Chemistry WebBook:  A Chemical Data Resource on the Internet
journal, September 2001

  • Linstrom, Peter J.; Mallard, William G.
  • Journal of Chemical & Engineering Data, Vol. 46, Issue 5
  • DOI: 10.1021/je000236i

Anisotropy and asymmetry of the polarizability of anthracene, studied by NMR
journal, July 1986

  • Ruessink, B. H.; MacLean, C.
  • The Journal of Chemical Physics, Vol. 85, Issue 1
  • DOI: 10.1063/1.451601

Improvements in the orbitalwise scaling down of Perdew–Zunger self-interaction correction in many-electron regions
journal, May 2020

  • Yamamoto, Yoh; Romero, Selim; Baruah, Tunna
  • The Journal of Chemical Physics, Vol. 152, Issue 17
  • DOI: 10.1063/5.0004738

Organic electroluminescent diodes
journal, September 1987

  • Tang, C. W.; VanSlyke, S. A.
  • Applied Physics Letters, Vol. 51, Issue 12
  • DOI: 10.1063/1.98799

Real-space post-Hartree–Fock correlation models
journal, February 2005

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 122, Issue 6
  • DOI: 10.1063/1.1844493

How well do static electronic dipole polarizabilities from gas-phase experiments compare with density functional and MP2 computations?
journal, October 2015

  • Thakkar, Ajit J.; Wu, Taozhe
  • The Journal of Chemical Physics, Vol. 143, Issue 14
  • DOI: 10.1063/1.4932594

Benchmark theoretical study of the ionization threshold of benzene and oligoacenes
journal, August 2003

  • Deleuze, M. S.; Claes, L.; Kryachko, E. S.
  • The Journal of Chemical Physics, Vol. 119, Issue 6
  • DOI: 10.1063/1.1589731

Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981


Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction
journal, July 2019


Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms
journal, February 2015

  • Pederson, Mark R.
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907592

Many-electron self-interaction error in approximate density functionals
journal, November 2006

  • Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
  • The Journal of Chemical Physics, Vol. 125, Issue 20
  • DOI: 10.1063/1.2403848

Light-emitting diodes based on conjugated polymers
journal, October 1990

  • Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.
  • Nature, Vol. 347, Issue 6293
  • DOI: 10.1038/347539a0

Density functional studies of the dipole polarizabilities of the linear polyacenes benzene through nonacene
journal, June 2005

  • Hinchliffe, Alan; Nikolaidi, Beatrice; Soscún Machado, Humberto
  • Open Chemistry, Vol. 3, Issue 2
  • DOI: 10.2478/bf02476002

Molecular polarizabilities from the Cotton-Mouton effect
journal, January 1972

  • Cheng, Cl; Murthy, Dsn; Ritchie, Gld
  • Australian Journal of Chemistry, Vol. 25, Issue 6
  • DOI: 10.1071/ch9721301

Relationship between the highest occupied Kohn-Sham orbital eigenvalue and ionization energy
journal, August 1999


Self-interaction-free exchange-correlation functional for thermochemistry and kinetics
journal, March 2006

  • Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
  • The Journal of Chemical Physics, Vol. 124, Issue 9
  • DOI: 10.1063/1.2179072

Influence of the exchange-correlation potential in density-functional calculations on polarizabilities and absorption spectra of alkali-metal clusters
journal, May 2001


Fractional occupation numbers and self‐interaction correction‐scaling methods with the Fermi‐Löwdin orbital self‐interaction correction approach
journal, May 2020

  • Aquino, Fredy W.; Shinde, Ravindra; Wong, Bryan M.
  • Journal of Computational Chemistry, Vol. 41, Issue 12
  • DOI: 10.1002/jcc.26168

Electron-correlation effects on the static longitudinal polarizability of polymeric chains
journal, July 1995

  • Champagne, Benoît; Mosley, David H.; Vrac̆ko, Marjan
  • Physical Review A, Vol. 52, Issue 1
  • DOI: 10.1103/physreva.52.178

Self-Interaction Corrections Within the Fermi-Orbital-Based Formalism
book, July 2015


Time-dependent density functional theory calculation of van der Waals coefficient of sodium clusters
journal, October 2007

  • Banerjee, Arup; Chakrabarti, Aparna; Ghanty, Tapan K.
  • The Journal of Chemical Physics, Vol. 127, Issue 13
  • DOI: 10.1063/1.2774976

Communication: Self-interaction correction with unitary invariance in density functional theory
journal, March 2014

  • Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P.
  • The Journal of Chemical Physics, Vol. 140, Issue 12
  • DOI: 10.1063/1.4869581

Quadratically convergent calculation of localized molecular orbitals
journal, January 1982

  • Leonard, Joseph M.; Luken, William L.
  • Theoretica Chimica Acta, Vol. 62, Issue 2
  • DOI: 10.1007/bf00581477

High-resolution laser spectroscopy on the S1←S0 transition of jet-cooled anthracene: Rotational structure and Stark effect
journal, December 2007

  • Bendkowsky, Vera; Heinecke, Elke; Hese, Achim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2806184

Ab initio studies of structures and properties of small potassium clusters
text, January 2008