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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.
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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. https://doi.org/10.1073/pnas.1711126115
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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. https://doi.org/10.1073/pnas.1711126115.
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@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}
}
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Journal Article:
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https://doi.org/10.1073/pnas.1711126115
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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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