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Title: Low-lying excited states in crystalline perylene

Abstract

Organic materials are promising candidates for advanced optoelectronics and are used in light-emitting diodes and photovoltaics. However, the underlying mechanisms allowing the formation of excited states responsible for device functionality, such as exciton generation and charge separation, are insufficiently understood. This is partly due to the wide range of existing crystalline polymorphs depending on sample preparation conditions. Here, we determine the linear optical response of thin-film single-crystal perylene samples of distinct polymorphs in transmission and reflection geometries. The sample quality allows for unprecedented high-resolution spectroscopy, which offers an ideal opportunity for judicious comparison between theory and experiment. Excellent agreement with first-principles calculations for the absorption based on the GW plus Bethe–Salpeter equation (GW-BSE) approach of many-body perturbation theory (MBPT) is obtained, from which a clear picture of the low-lying excitations in perylene emerges, including evidence of an exciton–polariton stopband, as well as an assessment of the commonly used Tamm–Dancoff approximation to the GW-BSE approach. Furthermore, our findings on this well-controlled system can guide understanding and development of advanced molecular solids and functionalization for applications.

Authors:
; ; ; ; ; ; ORCiD logo; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1414876
Alternate Identifier(s):
OSTI ID: 1466699
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 2; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; molecular crystals; many-body perturbation theory; excited states; spectroscopy

Citation Formats

Rangel, Tonatiuh, Rinn, Andre, Sharifzadeh, Sahar, da Jornada, Felipe H., Pick, André, Louie, Steven G., Witte, Gregor, Kronik, Leeor, Neaton, Jeffrey B., and Chatterjee, Sangam. Low-lying excited states in crystalline perylene. United States: N. p., 2017. Web. doi:10.1073/pnas.1711126115.
Rangel, Tonatiuh, Rinn, Andre, Sharifzadeh, Sahar, da Jornada, Felipe H., Pick, André, Louie, Steven G., Witte, Gregor, Kronik, Leeor, Neaton, Jeffrey B., & Chatterjee, Sangam. Low-lying excited states in crystalline perylene. United States. doi:10.1073/pnas.1711126115.
Rangel, Tonatiuh, Rinn, Andre, Sharifzadeh, Sahar, da Jornada, Felipe H., Pick, André, Louie, Steven G., Witte, Gregor, Kronik, Leeor, Neaton, Jeffrey B., and Chatterjee, Sangam. Tue . "Low-lying excited states in crystalline perylene". United States. doi:10.1073/pnas.1711126115.
@article{osti_1414876,
title = {Low-lying excited states in crystalline perylene},
author = {Rangel, Tonatiuh and Rinn, Andre and Sharifzadeh, Sahar and da Jornada, Felipe H. and Pick, André and Louie, Steven G. and Witte, Gregor and Kronik, Leeor and Neaton, Jeffrey B. and Chatterjee, Sangam},
abstractNote = {Organic materials are promising candidates for advanced optoelectronics and are used in light-emitting diodes and photovoltaics. However, the underlying mechanisms allowing the formation of excited states responsible for device functionality, such as exciton generation and charge separation, are insufficiently understood. This is partly due to the wide range of existing crystalline polymorphs depending on sample preparation conditions. Here, we determine the linear optical response of thin-film single-crystal perylene samples of distinct polymorphs in transmission and reflection geometries. The sample quality allows for unprecedented high-resolution spectroscopy, which offers an ideal opportunity for judicious comparison between theory and experiment. Excellent agreement with first-principles calculations for the absorption based on the GW plus Bethe–Salpeter equation (GW-BSE) approach of many-body perturbation theory (MBPT) is obtained, from which a clear picture of the low-lying excitations in perylene emerges, including evidence of an exciton–polariton stopband, as well as an assessment of the commonly used Tamm–Dancoff approximation to the GW-BSE approach. Furthermore, our findings on this well-controlled system can guide understanding and development of advanced molecular solids and functionalization for applications.},
doi = {10.1073/pnas.1711126115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 2,
volume = 115,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1711126115

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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: Perylene single-crystal samples and structure: Microscopy images of (100)-oriented perylene single crystals in the α-phase (Top) and the β-phase (Bottom) (A), identifiable by their respective characteristic nearly rectangular and rhombic shapes. The crystalline axes given by the arrows are universal for A–C; the depicted crystals are correctly alignedmore » to the shown molecular packing motives. Molecular orientation in α-phase perylene is found in B. The unit cell contains four molecules (red oval), where pairs of parallelly oriented molecules form a dimeric herringbone motif. The corresponding picture for the β-phase is presented in C. Its unit cell comprises two molecules forming a standard herringbone stacking pattern (blue oval). The light field is incident along the depicted $\vec{a}^*$ axis. The linear absorption spectrum of perylene in the vapor phase is displayed in D. The HOMO–LUMO transition is assigned at 2.98 eV. Linear combinations of two vibrons with energies of 42 and 164meV lead to a series of vibronic progressions. The Inset shows the perylene molecule and the alignment of the transition dipole moment (TDM) for the known HOMO–LUMO transition.« less

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Works referenced in this record:

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

Anisotropic optical properties of single crystalline PTCDA studied by spectroscopic ellipsometry
journal, March 2002


Gap renormalization of molecular crystals from density-functional theory
journal, August 2013


Recent Advances in Singlet Fission
journal, April 2013


Quasiparticle and optical spectroscopy of the organic semiconductors pentacene and PTCDA from first principles
journal, March 2012


A Star-Shaped Perylene Diimide Electron Acceptor for High-Performance Organic Solar Cells
journal, March 2014


BerkeleyGW: A massively parallel computer package for the calculation of the quasiparticle and optical properties of materials and nanostructures
journal, June 2012

  • Deslippe, Jack; Samsonidze, Georgy; Strubbe, David A.
  • Computer Physics Communications, Vol. 183, Issue 6
  • DOI: 10.1016/j.cpc.2011.12.006

Excitonic Effects on the Silicon Plasmon Resonance
journal, June 2001


Optical differential reflectance spectroscopy on thin molecular films
journal, January 2012

  • Forker, Roman; Gruenewald, Marco; Fritz, Torsten
  • Annual Reports Section "C" (Physical Chemistry), Vol. 108
  • DOI: 10.1039/c2pc90002e

The role of polymorphism in organic thin films: oligoacenes investigated from first principles
journal, December 2009


Recent developments in the ABINIT software package
journal, August 2016


Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986


Molecular Packing Determines Singlet Exciton Fission in Organic Semiconductors
journal, June 2014

  • Kolata, Kolja; Breuer, Tobias; Witte, Gregor
  • ACS Nano, Vol. 8, Issue 7
  • DOI: 10.1021/nn502544d

Structure preserving parallel algorithms for solving the Bethe–Salpeter eigenvalue problem
journal, January 2016

  • Shao, Meiyue; da Jornada, Felipe H.; Yang, Chao
  • Linear Algebra and its Applications, Vol. 488
  • DOI: 10.1016/j.laa.2015.09.036

Excited-State Properties of Molecular Solids from First Principles
journal, May 2016


Towards a Complete Description of a Polymorphic Crystal: The Example of Perylene
journal, April 2003

  • Botoshansky, Mark; Herbstein, Frank H.; Kapon, Moshe
  • Helvetica Chimica Acta, Vol. 86, Issue 4
  • DOI: 10.1002/hlca.200390097

First-Principles Theory of Quasiparticles: Calculation of Band Gaps in Semiconductors and Insulators
journal, September 1985


Polymorph-Selective Preparation and Structural Characterization of Perylene Single Crystals
journal, October 2015

  • Pick, André; Klues, Michael; Rinn, Andre
  • Crystal Growth & Design, Vol. 15, Issue 11
  • DOI: 10.1021/acs.cgd.5b01130

Electronic excitations: density-functional versus many-body Green’s-function approaches
journal, June 2002


Oligoacene exciton binding energies: Their dependence on molecular size
journal, February 2005


Vibrational spectroscopy of solid state molecular dimers
journal, March 1983


Molecular Understanding of Organic Solar Cells: The Challenges
journal, November 2009

  • Brédas, Jean-Luc; Norton, Joseph E.; Cornil, Jérôme
  • Accounts of Chemical Research, Vol. 42, Issue 11
  • DOI: 10.1021/ar900099h

Optical Reflection Spectroscopy of Organic Solids
journal, October 1980


Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates
journal, September 1963


Structural and excited-state properties of oligoacene crystals from first principles
journal, March 2016


Low-Energy Charge-Transfer Excitons in Organic Solids from First-Principles: The Case of Pentacene
journal, June 2013

  • Sharifzadeh, Sahar; Darancet, Pierre; Kronik, Leeor
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 13
  • DOI: 10.1021/jz401069f

Large-scale complementary integrated circuits based on organic transistors
journal, February 2000

  • Crone, B.; Dodabalapur, A.; Lin, Y. -Y.
  • Nature, Vol. 403, Issue 6769, p. 521-523
  • DOI: 10.1038/35000530

Polaritons: the electromagnetic modes of media
journal, July 1974


Structural and electronic properties of perylene from first principles calculations
journal, March 2013

  • Fedorov, I. A.; Zhuravlev, Y. N.; Berveno, V. P.
  • The Journal of Chemical Physics, Vol. 138, Issue 9
  • DOI: 10.1063/1.4794046

Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS-Pentacene
journal, December 2014

  • Sharifzadeh, Sahar; Wong, Cathy Y.; Wu, Hao
  • Advanced Functional Materials, Vol. 25, Issue 13
  • DOI: 10.1002/adfm.201403005

Spectral Effects of Strong Exciton Coupling in the Lowest Electronic Transition of Perylene
journal, May 1964

  • Hochstrasser, Robin M.
  • The Journal of Chemical Physics, Vol. 40, Issue 9
  • DOI: 10.1063/1.1725563

Cavity ring-down spectroscopy and theoretical calculations of the S1(B3u1)←S0(Ag1) transition of jet-cooled perylene
journal, February 2005

  • Tan, Xiaofeng; Salama, Farid
  • The Journal of Chemical Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.1851502

Molecular Aggregate Photophysics beyond the Kasha Model: Novel Design Principles for Organic Materials
journal, January 2017


Electrical and Optical Properties of a Stable Synthetic Metallic Polymer: Polypyrrole
journal, August 1981

  • Watanabe, Atsushi; Tanaka, Masashi; Tanaka, Jiro
  • Bulletin of the Chemical Society of Japan, Vol. 54, Issue 8
  • DOI: 10.1246/bcsj.54.2278

Vibronic structure of PTCDA stacks: the exciton–phonon-charge-transfer dimer
journal, July 1999


Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks
journal, December 2015

  • Hestand, Nicholas J.; Spano, Frank C.
  • The Journal of Chemical Physics, Vol. 143, Issue 24
  • DOI: 10.1063/1.4938012

Exciton dispersion in molecular solids
journal, March 2015


Exciton-Plasmon States in Nanoscale Materials: Breakdown of the Tamm−Dancoff Approximation
journal, August 2009

  • Grüning, Myrta; Marini, Andrea; Gonze, Xavier
  • Nano Letters, Vol. 9, Issue 8
  • DOI: 10.1021/nl803717g

Magnetic Field Splitting and Dispersion of the Lower 1S-Exciton Polariton in KI and RbI
journal, March 1990

  • Fröhlich, D.; Kirchhoff, St.; Köhler, P.
  • physica status solidi (b), Vol. 158, Issue 1
  • DOI: 10.1002/pssb.2221580126

Quasi-metallic reflection spectra of TCNQ single crystals
journal, January 1976


Solid-state optical absorption from optimally tuned time-dependent range-separated hybrid density functional theory
journal, August 2015


From organic metals to superconductors: managing conduction electrons in organic solids
journal, June 1984


Crystallochromy of perylene pigments: Interference between Frenkel excitons and charge-transfer states
journal, September 2009


Ab initio calculation of the electronic and optical properties of solid pentacene
journal, March 2003


The polarized reflection and absorption spectra of perylene crystals in monomeric and dimeric forms
journal, October 1976


Electronic Spectra of Perylene and Coronene Evaporated Films as a Function of Their Crystallinity
journal, February 1976

  • Kamura, Yusuke; Shirotani, Ichimin; Ohno, Koichi
  • Bulletin of the Chemical Society of Japan, Vol. 49, Issue 2
  • DOI: 10.1246/bcsj.49.418

Ab Initio Optoelectronic Properties of Silicon Nanoparticles: Excitation Energies, Sum Rules, and Tamm–Dancoff Approximation
journal, June 2014

  • Rocca, Dario; Vörös, Márton; Gali, Adam
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 8
  • DOI: 10.1021/ct5000956

Excimer emission of anthracene, perylene, coronene and pyrene microcrystals dispersed in water
journal, July 1998


AB-INITIO STUDY ON THE EXCITON BINDING ENERGIES IN ORGANIC SEMICONDUCTORS
journal, March 2006

  • Hummer, Kerstin; Puschnig, Peter; Sagmeister, Stephan
  • Modern Physics Letters B, Vol. 20, Issue 06
  • DOI: 10.1142/S0217984906010603

Excitons in molecular crystals from first-principles many-body perturbation theory: Picene versus pentacene
journal, November 2012


Electron-hole excitations and optical spectra from first principles
journal, August 2000


Absorption and emission spectroscopy of perylene (C20H12) isolated in Ne, Ar, and N2 matrices
journal, April 1999

  • Joblin, C.; Salama, F.; Allamandola, L.
  • The Journal of Chemical Physics, Vol. 110, Issue 15
  • DOI: 10.1063/1.478631

Lowest Optical Excitations in Molecular Crystals: Bound Excitons versus Free Electron-Hole Pairs in Anthracene
journal, April 2004


    Works referencing / citing this record:

    The GW Compendium: A Practical Guide to Theoretical Photoemission Spectroscopy
    journal, July 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.