The separation of vibrational coherence from ground- and excited-electronic states in P3HT film

Abstract
© 2015 AIP Publishing LLC. Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S (λ 1, T∼ 2, λ 3)) along the population time (T∼ 2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S (λ 1, ν∼ 2, λ 3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ ν∼ 2) in the rephasing beating map and at negative frequency (- ν∼ 2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.

Citation
Song Y, Hellmann C, Stingelin N, Scholes GD (2015) The separation of vibrational coherence from ground- and excited-electronic states in P3HT film. J Chem Phys 142: 212410. Available: http://dx.doi.org/10.1063/1.4916325.

Acknowledgements
G.D.S. acknowledges financial support for this work from the Natural Sciences and Engineering Research Council of Canada (through NSERC Polanyi Award). Y.S. would like to thank Dr. Ryan D. Pensack for stimulating discussion. C.H. was supported by a KAUST Global Collaborative Research Academic Excellence Alliance (AEA) grant.

Publisher
AIP Publishing

Journal
The Journal of Chemical Physics

DOI
10.1063/1.4916325

PubMed ID
26049430

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