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Title: Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission

Abstract

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Department of Chemistry, University of Minnesota, Minneapolis, USA
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1414320
Alternate Identifier(s):
OSTI ID: 1505511; OSTI ID: 1594954
Grant/Contract Number:  
SC0018203
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 5; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hart, Stephanie M., Silva, W. Ruchira, and Frontiera, Renee R. Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission. United Kingdom: N. p., 2018. Web. doi:10.1039/C7SC03496B.
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Hart, Stephanie M., Silva, W. Ruchira, & Frontiera, Renee R. Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission. United Kingdom. https://doi.org/10.1039/C7SC03496B
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Hart, Stephanie M., Silva, W. Ruchira, and Frontiera, Renee R. Mon . "Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission". United Kingdom. https://doi.org/10.1039/C7SC03496B.
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@article{osti_1414320,
title = {Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission},
author = {Hart, Stephanie M. and Silva, W. Ruchira and Frontiera, Renee R.},
abstractNote = {Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.},
doi = {10.1039/C7SC03496B},
journal = {Chemical Science},
number = 5,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
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https://doi.org/10.1039/C7SC03496B
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Cited by: 56 works
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Figures / Tables:

Fig. 1 Fig. 1: Characterization of pentacene samples used for FSRS experiments. (a) Structure of pentacene in a herringbone structure characteristic of this crystalline solid. (b) Image of crystal used in the FSRS experiments, grown by physical vapor transport. (c) Spontaneous ground state Raman spectrum of crystalline pentacene at 633 nm excitation.
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