title: Visualizing Excited-State Dynamics of a Diaryl Thiophene: Femtosecond Stimulated Raman Scattering as a Probe of Conjugated Molecules.
abstract: Conjugated organic polymers based on substituted thiophene units are versatile building blocks of many photoactive materials, such as photochromic molecular switches or solar energy conversion devices. Unraveling the different processes underlying their photochemistry, such as the evolution on different electronic states and multidimensional structural relaxation, is a challenge critical to defining their function. Using femtosecond stimulated Raman scattering (FSRS) supported by quantum chemical calculations, we visualize the reaction pathway upon photoexcitation of the model compound 2-methyl-5-phenylthiophene. Specifically, we find that the initial wavepacket dynamics of the reaction coordinates occurs within the first ≈1.5 ps, followed by a ≈10 ps thermalization. Subsequent slow opening of the thiophene ring through a cleavage of the carbon-sulfur bond triggers an intersystem crossing to the triplet excited state. Our work demonstrates how a detailed mapping of the excited-state dynamics can be obtained, combining simultaneous structural sensitivity and ultrafast temporal resolution of FSRS with the chemical information provided by time-dependent density functional theory calculations.
authors.affiliation: Dipartimento di Fisica, Universitá di Roma "La Sapienza" , Roma I-00185, Italy.|Dipartimento di Scienze Fisiche e Chimiche, Universitá degli Studi dell'Aquila , L'Aquila I-67100, Italy.
authors.forename: Giovanni
authors.initials: G
authors.lastname: Batignani
authors.affiliation: Dipartimento di Fisica, Universitá di Roma "La Sapienza" , Roma I-00185, Italy.
authors.forename: Emanuele
authors.initials: E
authors.lastname: Pontecorvo
authors.affiliation: Dipartimento di Fisica, Universitá di Roma "La Sapienza" , Roma I-00185, Italy.
authors.forename: Carino
authors.initials: C
authors.lastname: Ferrante
authors.affiliation: Dipartimento di Scienze Fisiche e Chimiche, Universitá degli Studi dell'Aquila , L'Aquila I-67100, Italy.
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Aschi
authors.affiliation: Department of Chemistry, University of Kansas , Lawrence, Kansas 66045, United States.
authors.forename: Christopher G
authors.initials: CG
authors.lastname: Elles
authors.affiliation: Dipartimento di Fisica, Universitá di Roma "La Sapienza" , Roma I-00185, Italy.|Center for Life Nano Science @Sapienza, Istituto Italiano di Tecnologia , Roma I-00161, Italy.
authors.forename: Tullio
authors.initials: T
authors.lastname: Scopigno