Monday, October 9, 2017

Benzophenone Ultrafast Triplet Population: Revisiting the Kinetic Model by Surface-Hopping Dynamics

Marco Marazzi, Sebastian Mai, Daniel Roca-Sanjuán, Mickaël G. Delcey, Roland Lindh, Leticia González, and Antonio Monari (2016)
Highlighted by Ravi Kumar Venkatraman

In 1967, Norrish and Porter were honoured with Nobel prize for their seminal work on understanding the fast chemical reactions using flash photolysis technique.1 Since then benzophenone (Bzp) serves as an archetypal system for understanding the photochemistry of various aromatic ketones. Aromatic ketones find their use in various technologically significant applications like sunscreen, photocatalysis, etc., apart from their fundamental interest.2 Efficacy of aromatic ketones for use in various applications relies upon their photophysics and photochemistry. Therefore, understanding the photophysics and photochemistry of Bzp has attracted several experimental and theoretical investigations.2 Despite these myriads of investigations, pathways for populating the lowest triplet state (T1) after photoexcitation to the S1 state remains still elusive. There are two plausible pathways: i) a direct ISC from S1(nπ*) to T1(nπ*); or ii) an indirect process, involving ISC from S1(nπ*) to T1(ππ*) with subsequent internal conversion (IC) to T1(nπ*). The latter pathway is more efficient, according to El-Sayed’s rule, because it entails a change in the orbital character during the spin-orbit coupling mediated process.3

Reproduced with permission from Marco Marazzi, Sebastian Mai, et. al., J. Phys. Chem. Lett., 7, 622 (2016) under Creative Commons Attribution (CC-BY) License

In this work, authors have employed ab initio surface-hopping dynamics simulation for Bzp in gas phase to explore the pathways for the lowest triplet state (T1) population after photo-excitation to the S1 state. This study clearly demonstrates that the dominant mechanism for populating the T1 state is the indirect pathway invoking T2 state as an intermediate. This study urges reinvestigation of spectroscopic assignment for Bzp in various time-resolved spectroscopic techniques. Furthermore, the mechanism for the photoinduced energy transfer in photocatalysis and DNA damage studies must be revisited as in principle now both channels involving T2 and T1 states are available.

1.) F. Ariese, K. Roy, V. R. Kumar, H. C. Sudeeksha, S. Kayal, S. Umapathy, Time-Resolved Spectroscopy: Instrumentation and Applications in Encyclopedia of Analytical Chemistry, edited by R. A. Meyers, 1-55, (2017) John Wiley & Sons, Ltd.
2.) M. C. Cuquerella, V. L-Vallet, J. Cadet, and M. A. Miranda, Benzophenone Photosensitized DNA Damage, Acc. Chem. Res., 45, 1558 (2012).
3.) Elsayed, M. A., Spin-Orbit Coupling and Radiationless Processes in Nitrogen Heterocyclics. J. Chem. Phys., 38, 2834 (1963).