Bernhard Felix Lang

Ultrafast Photochemistry in Liquids

Ultrafast photochemical processes can occur in parallel with the relaxation of the optically populated excited state toward equilibrium. The latter involves both intra- and intermolecular modes, namely vibrational and solvent coordinates, and takes place on timescales ranging from a few tens of femtoseconds to up to hundreds of picoseconds, depending on the system. As a consequence, the reaction dynamics can substantially differ from those usually measured with slower photoinduced processes occurring from equilibrated excited states. For example, the decay of the excited-state population may become strongly nonexponential and depend on the excitation wavelength, contrary to the Kasha and Vavilov rules. In this article, we first give a brief account of our current understanding of vibrational and solvent relaxation processes. We then present an overview of important classes of ultrafast photochemical reactions, namely electron and proton transfer as well as isomerization, and illustrate with several examples how nonequilibrium effects can affect their dynamics.

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha-Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis-trans isomerizations, respectively.

Acylgermanes: Photoinitiators and Sources for Ge-Centered Radicals. Insights into their Reactivity

Acylgermanes have been shown to act as efficient photoinitiators. In this investigation we show how dibenzoyldiethylgermane 1 reacts upon photoexcitation. Our real-time investigation utilizes femto- and nanosecond transient absorption, time-resolved EPR (50 ns), photo-chemically induced dynamic nuclear polarization, DFT calculations, and GC-MS analysis. The benzoyldiethylgermyl radical G• is formed via the triplet state of parent 1. On the nanosecond time scale this radical can recombine or undergo hydrogen-transfer reactions. Radical G• reacts with butyl acrylate at a rate of 1.2 ± 0.1 × 10(8) and 3.2 ± 0.2 × 10(8) M(-1) s(-1), in toluene and acetonitrile, respectively. This is ~1 order of magnitude faster than related phosphorus-based radicals. The initial germyl and benzoyl radicals undergo follow-up reactions leading to oligomers comprising Ge-O bonds. LC-NMR analysis of photocured mixtures containing 1 and the sterically hindered acrylate 3,3-dimethyl-2-methylenebutanoate reveals that the products formed in the course of a polymerization are consistent with the intermediates established at short time scales.

Real-Time Observation of the Formation of Excited Radical Ions in Bimolecular Photoinduced Charge Separation: Absence of the Marcus Inverted Region Explained

Unambiguous evidence for the formation of excited ions upon ultrafast bimolecular photoinduced charge separation is found using a combination of femtosecond time-resolved fluorescence up-conversion, infrared and visible transient absorption spectroscopy. The reaction pathways are tracked by monitoring the vibrational energy redistribution in the product after charge separation and subsequent charge recombination. For moderately exergonic reactions, both donor and acceptor are found to be vibrationally hot, pointing to an even redistribution of the energy dissipated upon charge separation and recombination in both reaction partners. For highly exergonic reactions, the donor is very hot, whereas the acceptor is mostly cold. The asymmetric energy redistribution is due to the formation of the donor cation in an electronic excited state upon charge separation, confirming one of the hypotheses for the absence of the Marcus inverted region in photoinduced bimolecular charge separation processes.

Broadband ultraviolet-visible transient absorption spectroscopy in the nanosecond to microsecond time domain with sub-nanosecond time resolution

A combination of sub-nanosecond photoexcitation and femtosecond supercontinuum probing is used to extend femtosecond transient absorption spectroscopy into the nanosecond to microsecond time domain. Employing a passively Q-switched frequency tripled Nd:YAG laser and determining the jitter of the time delay between excitation and probe pulses with a high resolution time delay counter on a single-shot basis leads to a time resolution of 350 ps in picosecond excitation mode. The time overlap of almost an order of magnitude between fs and sub-ns excitation mode permits to extend ultrafast transient absorption (TA) experiments seamlessly into time ranges traditionally covered by laser flash photolysis. The broadband detection scheme eases the identification of intermediate reaction products which may remain undetected in single-wavelength detection flash photolysis arrangements. Single-shot referencing of the supercontinuum probe with two identical spectrometer/CCD arrangements yields an excellent signal-to-noise ratio for the so far investigated chromophores in short to moderate accumulation times.

Photometrics of ultrafast and fast broadband electronic transient absorption spectroscopy: State of the art

The physical limits of the photometric resolution in broadband electronic transient absorption spectroscopy are discussed together with solutions for how to reach these limits in practice. In the first part, quantitative expressions for the noise contributions to the transient absorption signal are derived and experimentally tested. Experimental approaches described in the literature are discussed and compared on this basis. Guide-lines for designing a setup are established. In the second part, a method for obtaining nearly shot-noise limited kinetics with photometric resolution of the order of 100 μOD in overall measurement times of a few minutes from femtosecond to microsecond time scale is presented. The results are discussed in view of other experiments of step-scan type which are subject to a background or to correlated noise. Finally, detailed information is provided on how to obtain transient absorption spectra where counting statistics are the sole source of noise. A method for how to suppress outliers without introducing bias is discussed. An application example is given to demonstrate the achievable signal-to-noise level and the fast acquisition time.

Model-free Investigation of Ultrafast Bimolecular Chemical Reactions: Bimolecular Photoinduced Electron Transfer

Using photoinduced bimolecular electron transfer reactions as example we demonstrate how diffusion controlled bimolecular chemical reactions can be studied in a model-free manner by quantitatively combining different ultrafast spectroscopical tools.

Femtosecond time-resolved studies on bimolecular electron transfer processes

Bimolecular photo-induced electron transfer between an electron donor and an electron acceptor in a polar solvent may result in the formation of free ions (FI). Weller and coworkers have invoked several types of intermediates for describing this process exciplex or contact ion pair (CIP), loose ion pair (LIP), also called solvent separated ion pair. The knowledge of the structures of these intermediates is fundamental for understanding the details of bimolecular reactions in solution. However, up to now, no spectroscopic technique has been able to differentiate them. The UV-Vis absorption spectra of the ion pairs and the free ions are very similar. Furthermore, previous time resolved resonant Raman investigations have shown that these species exhibit essentially the same high frequency vibrational spectrum. Therefore, a pump/pump-probe experiment is developed to obtain more informations on the structures of these geminate ion pairs. It allows the investigation of the excited states dynamics of the transient species at different time delays after photo triggering the charge transfer, by monitoring the ground state recovery (GSR) of those transient species. This chapter uses perylene (Pe) as fluorescer (electron donor) and either trans-1,2-dicyanoethylene (DCE) or 1,4-dicyanobenzene (DCB) as quencher (electron acceptor) in acetonitrile (ACN).