Understanding Ultrafast Dynamics of Conformation Specific Photo-Excitation: A Femtosecond Transient Absorption and Ultrafast Raman Loss Study

Roy, Khokan and Kayal, Surajit and Kumar, Venkatraman Ravi and Beeby, Andrew and Ariese, Freek and Umapathy, Siva (2017) Understanding Ultrafast Dynamics of Conformation Specific Photo-Excitation: A Femtosecond Transient Absorption and Ultrafast Raman Loss Study. In: JOURNAL OF PHYSICAL CHEMISTRY A, 121 (35). pp. 6538-6546.

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Abstract

Excited state ultrafast conformational reorganization is recognized as an important phenomenon that facilitates light-induced functions of many molecular systems. This report describes the femtosecond and picosecond conformational relaxation dynamics of middle-ring and terminal ring twisted conformers of the acetylene pi-conjugated system bis(phenylethynyl)benzene, a model system for molecular wires. Through excitation wavelength dependent, femtosecond-transient absorption measurements, we found that the middle-ring and terminal ring twisted conformers relax at femtosecond (400600 fs) and picosecond (2024 ps) time scales, respectively. Actinic pumping into the red flank of the absorption spectrum leads to excitation of primarily planar conformers, and results in very different excited state dynamics. In addition, ultrafast Raman loss spectroscopic studies revealed the vibrational mode dependent relaxation dynamics for different excitation wavelengths. To corroborate our experimental findings, DFT and time-dependent DFT calculations were carried out. The FranckCondon simulation indicated that the vibronic structure observed in the electronic absorption and the fluorescence spectra are due to progressions and combinations of several vibrational modes corresponding to the phenyl ring and the acetylenic groups. Furthermore, the middle ring torsional rotation matches the room-temperature electronic absorption, in stark contrast to the terminal ring torsional rotation. Finally, we show that the middle-ring twisted conformer undergoes femtosecond torsional planarization dynamic, whereas the terminal rings relax on a few tens of picosecond time scale.

Item Type:	Journal Article
Publication:	JOURNAL OF PHYSICAL CHEMISTRY A
Additional Information:	Copy right for this article belongs to the AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	07 Oct 2017 06:07
Last Modified:	07 Oct 2017 06:07
URI:	http://eprints.iisc.ac.in/id/eprint/57978

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