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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:
 [1];  [2];  [3];  [4];  [2];  [4]; ORCiD logo [2];  [5];  [6];  [7]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Philipps-Univ. Marburg, Marburg (Germany)
  3. Boston Univ., Boston, MA (United States)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Weizmann Institute of Science, Rehovoth (Israel)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, CA (United States)
  7. Philipps-Univ. Marburg, Marburg (Germany); Justus Liebig Univ. Giessen, Giessen (Germany)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1414876
Alternate Identifier(s):
OSTI ID: 1466699
Grant/Contract Number:  
AC02-05CH11231; No. DE- AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
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, Andre, 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, Andre, 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, Andre, 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, Andre 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 = {Tue Dec 26 00:00:00 EST 2017},
month = {Tue Dec 26 00:00:00 EST 2017}
}

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

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