TY - JOUR
T1 - Low-lying excited states in crystalline perylene
AU - Rangel, Tonatiuh
AU - Rinn, Andre
AU - Sharifzadeh, Sahar
AU - da Jornada, Felipe H.
AU - Pick, Andre
AU - Louie, Steven G.
AU - Witte, Gregor
AU - Kronik, Leeor
AU - Neaton, Jeffrey B.
AU - Chatterjee, Sangam
N1 - We acknowledge the use of computational resources at the National Energy Research Scientific Computing Center. Work at University of California, Berkeley, and Lawrence Berkeley National Laboratory was supported by the Center for Computational Study of Excited State Phenomena in Energy Materials at the Lawrence Berkeley National Laboratory, which is funded by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract DE-AC02-05CH11231, as part of the Computational Materials Sciences Program. The Marburg group acknowledges financial support through the German Science Foundation (DFG) though Projects A2 (to G.W.) and B2 (to A.R.) of the Coordinated Research Center 1083, the Graduate College 1782 (to A.P.). Work at the Weizmann Institute is supported by the United States–Israel Binational Science Foundation. This work is also supported by the Molecular Foundry through the US Department of Energy, Office of Basic Energy Sciences, under the same contract number. The work at Giessen is partially supported through Projects CH660/2 and CH660/3 (to S.C.) of the DFG. Author contributions: S.G.L., G.W., L.K., J.B.N., and S.C. designed research; T.R., A.R., S.S., F.H.J., A.P., S.G.L., G.W., L.K., J.B.N., and S.C. performed research; T.R., A.R., S.S., F.H.J., A.P., S.G.L., G.W., L.K., J.B.N., and S.C. analyzed data; and T.R., S.S., F.H.J., S.G.L., L.K., J.B.N., and S.C. wrote the paper.
PY - 2018/1/9
Y1 - 2018/1/9
N2 - 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. Our findings on this well-controlled system can guide understanding and development of advanced molecular solids and functionalization for applications.
AB - 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. Our findings on this well-controlled system can guide understanding and development of advanced molecular solids and functionalization for applications.
UR - http://www.scopus.com/inward/record.url?scp=85040249002&partnerID=8YFLogxK
U2 - 10.1073/pnas.1711126115
DO - 10.1073/pnas.1711126115
M3 - مقالة
SN - 0027-8424
VL - 115
SP - 284
EP - 289
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 2
ER -