Published: May 23, 2011 r2011 American Chemical Society 7550 dx.doi.org/10.1021/jp202277t | J. Phys. Chem. A 2011, 115, 7550–7558 ARTICLE pubs.acs.org/JPCA Ultrafast Branching of Reaction Pathways in 2-(2 0 -Hydroxyphenyl)benzothiazole in Polar Acetonitrile Solution Omar F. Mohammed, † Sandra Luber, ‡ Victor S. Batista, ‡ and Erik T. J. Nibbering* ,† † Max Born Institut f€ ur Nichtlineare Optik und Kurzzeitspektroskopie, Max Born Strasse 2A, D-12489 Berlin, Germany ‡ Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States 1. INTRODUCTION Branching of chemical reactions means a multiple outcome in reaction products. For molecular reactants converting into products in their respective electronic ground states, branching may be caused by the existence of several energetically accessible states. 1,2 Photoinduced reactions exhibiting branching into sev- eral products are less numerous. Even though the observation of state-selective quantum yield for reaction products has been reported, 3 the number of studies on the time-resolved observa- tion of the formation dynamics of different (transient) molecular product species have remained scarce. Here one can distinguish between cases where the different bond-breaking reaction chan- nels are chemically identical (see, e.g., refs 3À6) and a fully asymmetric outcome of the reactions, with chemically distinct products. 7,8 Optimal control of the outcome of chemical reaction dynamics has been pursued using amplitude and phase modu- lated excitation pulses on molecular systems. For midsized organic molecules, control has been hampered due to the onset of intramolecular vibrational redistribution (IVR). 9,10 Control of reaction dynamics in the condensed phase is even more difficult to achieve, as the soluteÀsolvent interactions often have much more impact on the molecular dynamical evolution than what can be achieved with preparation of excited states using laser pulses. In fact, soluteÀsolvent interactions have a profound influence on quantum yields of photoinduced trans/cis isomerizations, 11,12 much more than has been achieved with laser control experiments. 13À15 Until now, femtosecond studies of ultrafast branching pathway dynamics have mostly dealt with chemical bond disruption/formation, and less with other elementary chemical transformations such as electron, proton, or hydrogen transfer and trans/cis isomerizations. 16 In this work we report on the ultrafast photo- induced dynamics of 2-(2 0 -hydroxyphenyl)-benzothiazole (HBT) in acetonitrile (ACN). HBT is one of the benchmark systems for excited-state intramolecular hydrogen transfer (ESIHT). 17À27 Here the chemical reaction coordinate is that of enol f keto conversion by intramolecular hydrogen transfer (see Scheme 1) via an intramolecular hydrogen bond connecting the hydroxyphenyl and benzothiazole moieties. In nonpolar solvents, HBT solely exists in its enol form (twisting angle around the central bond connecting the hydroxyphenyl and benzothiazole moieties Θ =0°) with this intramolecular hydro- gen bond present. Photoinduced chemistry of HBT then exclu- sively implies electronic excitation of the enol(Θ =0°) state, followed by an ultrafast hydrogen transfer from enol*(Θ =0°) to keto*(Θ =0°) on a time scale of 60 fs. 19,21À27 A fluorescence signal with a high quantum yield (300 ps time constant 19 ) indicates the conversion of HBT into the keto(Θ =0°) electronic ground state, followed by intramolecular hydrogen back-transfer to the enol(Θ =0°) ground state, completing the photocycle. We now present experimental and theoretical results of analyzing the ultrafast dynamics of HBT in ACN, and conclude that even though in polar ACN HBT in the electronic ground state only exists in the enol(Θ =0°) geometry, electronic Received: March 10, 2011 Revised: May 22, 2011 ABSTRACT: In a combined study on the photophysics of 2-(2 0 -hydroxyphenyl)-benzothiazole (HBT) in polar acetoni- trile utilizing ultrafast infrared spectroscopy and quantum chemical calculations, we show that a branching of reaction pathways occurs on femtosecond time scales. Apart from the excited-state intramolecular hydrogen transfer (ESIHT) con- verting electronically excited enol tautomer into the keto tautomer, known to be the dominating mechanism of HBT in nonpolar solvents such as cyclohexane and tetrachloroethene, in acetonitrile solution twisting also occurs around the central CÀC bond connecting the hydroxyphenyl and benzothiazole units in both electronically excited enol and keto tautomers. The solvent-induced intramolecular twisting enables efficient internal conversion pathways to both enol and keto tautomers in the electronic ground state. Whereas relaxation to the most stable enol tautomer with twisting angle Θ =0° implies full ground state recovery, a small fraction of HBT molecules persists as the keto twisting conformer with the twisting angle Θ = 180° for delay times extending beyond 120 ps.