Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 9, Issue 7, Pages 1642-1648Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.8b00345
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- ERC [290966 CAPRI]
- Royal Society (London, U.K.)
- SERB (India)
- Council of Scientific and Industrial Research (CSIR)
- Defence Research and Development Organisation (DRDO)
- Department of Science and Technology (DST)
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Solvation plays a critical role in various physicochemical and biological processes. Here, the rate of intersystem crossing (ISC) of benzophenone from its S-1(n pi*) state to its triplet manifold of states is shown to be modified by hydrogen-bonding interactions with protic solvent molecules. We selectively photoexcite benzophenone with its carbonyl group either solvent coordinated or uncoordinated by tuning the excitation wavelength to the band center (lambda = 340 nm) or the long-wavelength edge (lambda = 380 nm) of its pi* <- n absorption band. A combination of ultrafast absorption and Raman spectroscopy shows that the hydrogen-bonding interaction increases the time constant for ISC from <200 fs to 1.7 +/- 0.2 ps for benzophenone in CH3OH. The spectroscopic evidence suggests that the preferred pathway for ISC is from the S-1(n pi) to the T-2(pi pi*) state, with the rate of internal conversion from T-2(pi pi*) to T-1(n pi*) controlled by solvent quenching of excess vibrational energy.
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