Measuring Intermolecular Excited State Geometry for Favorable Singlet Fission in Tetracene

Vong, Daniel; Maleki, Farahnaz; Novak, Eric C.; Daemen, Luke L.; Moulé, Adam J.

doi:10.1021/acs.jpclett.3c02343

Measuring Intermolecular Excited State Geometry for Favorable Singlet Fission in Tetracene

Journal Article · Thu Jan 25 00:00:00 EST 2024 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.3c02343· OSTI ID:2337960

^[1]; ^[2]; ^[3]; Daemen, Luke L. ^[3]; ^[2]

University of California, Davis, CA (United States); University of California, Davis
University of California, Davis, CA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Singlet fission (SF) is the process of converting an excited singlet to a pair of excited triplets. Harvesting two charges from a single photon has the potential to increase photovoltaic device efficiencies. Acenes, such as tetracene and pentacene, are model molecules for studying SF. Despite SF being an endoergic process for tetracene and exoergic for pentacene, both acenes exhibit near unity SF quantum efficiencies, raising questions about how tetracene can overcome the energy barrier. Here, we use recently developed instrumentation to measure inelastic neutron scattering (INS) while optically exciting the model molecules using two different excitation energies. The spectroscopic results reveal intermolecular structural relaxation due to the presence of a triplet excited state. Here, the structural dynamics of the combined excited state molecule and surrounding tetracene molecules are further studied using time-dependent density functional theory (TD-DFT), which shows that the singlet and triplet levels shift due to the excited state geometry, reducing the uphill energy barrier for SF to within kT.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)

Grant/Contract Number:: AC02-05CH11231; AC52-07NA27344; SC0014664; SC0023123

OSTI ID:: 2337960

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 5 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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