https://physique.cuso.ch/fileadmin/physique/document/2005_vanStokkum_lecturenotes.pdf

Global and target analysis of time-resolved spectra

In this paper we present the theory and implementation of analytic derivatives of time-dependent density functional theory (TDDFT) excited states energies, both in vacuo and including solvent effects by means of the polarizable continuum model. The method is applied to two case studies: p-nitroaniline and 4-(dimethyl)aminobenzonitrile. For both molecules PCM-TDDFT is shown to be successful in supporting the analysis of experimental data with useful insights for a better understanding of photophysical and photochemical pathways in solution.

Geometries and properties of excited states in the gas phase and in solution: theory and application of a time-dependent density functional theory polarizable continuum model.

The photophysical and photochemical reactions, after light absorption by a photosynthetic pigment-protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. The advent of ultrafast laser systems that produce pulses with femtosecond duration opened up a new area of research and enabled investigation of these photophysical and photochemical reactions in real time. Here, we provide a basic description of the ultrafast transient absorption technique, the laser and wavelength-conversion equipment, the transient absorption setup, and the collection of transient absorption data. Recent applications of ultrafast transient absorption spectroscopy on systems with increasing degree of complexity, from biomimetic light-harvesting systems to natural light-harvesting antennas, are presented. In particular, we will discuss, in this educational review, how a molecular understanding of the light-harvesting and photoprotective functions of carotenoids in photosynthesis is accomplished through the application of ultrafast transient absorption spectroscopy.

/pdf/ultrafast-transient-absorption-spectroscopy-principles-and-4k2hagdy5y.pdf

Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems.

Photocatalytic production of hydrogen peroxide (H2O2) on semiconductor catalysts with alcohol as a hydrogen source and molecular oxygen (O2) as an oxygen source is a potential method for safe H2O2 synthesis because the reaction can be carried out without the use of explosive H2/O2 mixed gases. Early reported photocatalytic systems, however, produce H2O2 with significantly low selectivity (∼1%). We found that visible light irradiation (λ > 420 nm) of graphitic carbon nitride (g-C3N4), a polymeric semiconductor, in an alcohol/water mixture with O2 efficiently produces H2O2 with very high selectivity (∼90%). Raman spectroscopy and electron spin resonance analysis revealed that the high H2O2 selectivity is due to the efficient formation of 1,4-endoperoxide species on the g-C3N4 surface. This suppresses one-electron reduction of O2 (superoxide radical formation), resulting in selective promotion of two-electron reduction of O2 (H2O2 formation).

http://pubs.acs.org/doi/pdf/10.1021/cs401208c

Highly Selective Production of Hydrogen Peroxide on Graphitic Carbon Nitride (g-C3N4) Photocatalyst Activated by Visible Light

Photoisomerization, that is, a photochemical reaction leading to a change of molecular structure after absorption of a photon, can have detrimental effects such as leading to DNA damage under solar irradiation, or as a limiting factor for the efficiency of solar cells. Here, we show that strong coupling of organic molecules to a confined light mode can be used to strongly suppress photoisomerization, as well as other photochemical reactions, and thus convert molecules that normally show fast photodegradation into photostable forms. We find this to be especially efficient in the case of collective strong coupling, where the distribution of a single excitation over many molecules and the light mode leads to a collective protection effect that almost completely suppresses the photochemical reaction.

Suppressing photochemical reactions with quantized light fields.

Pump--supercontinuum-probe (PSCP) spectroscopy with femtosecond time resolution is developed theoretically and experimentally. The connection to previous theoretical results on nonchirped probing is established. It is experimentally shown that the supercontinuum can be described as a single chirped pulse. A key problem of the technique---the precise time correction of transient spectra---is solved by monitoring the nonresonant electronic response from a pure solvent (liquids) or from a transparent substrate (solid films). This allows for an adequate characterization of the supercontinuum, in particular, for directly measuring the spectral dependence of the pump-probe cross correlation. For 50-fs pump pulses, a theoretical estimate gives an accuracy for the time correction of 10 fs, which is typically \ensuremath{\approx}1/30 of the supercontinuum pulse duration. Hence a time resolution of 10--20 fs can be experimentally realized. Contributions to the nonresonant transient signal from high-frequency Raman excitations and from low-frequency impulsive-stimulated Raman processes are discussed. The PSCP technique is illustrated by results from experiments with fused silica and several common solvents and with a chromophore in solution.

Femtosecond spectroscopy of condensed phases with chirped supercontinuum probing

The photoisomerization of azobenzene in solution was studied experimentally and by calculations. trans-to-cis and cis-to-trans dynamics are described through broadband transient absorption, fluorescence, and stimulated Raman spectroscopy. Transient absorption was extended to cover not only the nπ* band but also the ππ* band in the ultraviolet. Isomerization yields are used for a quantitative comparison of trans and cis transient spectra under different excitation. For the trans-to-cis path upon nπ*(S1) excitation, the evolution develops with 0.3, 3, and 16 ps. The first two times reflect population relaxation to a local minimum S1tL and subsequent transition to a dark intermediate S1tD over an 8 kJ/mol barrier. The existence of stationary points S1tL and S1tD is confirmed by quantum-chemical calculations. The third time corresponds to S1tD → S0 relaxation to the ground state via an S1/S0 conical intersection over a 12 kJ/mol barrier. Thus, the 16 ps time constant is attributed to the isomerization process...

Photoisomerization Dynamics and Pathways of trans- and cis-Azobenzene in Solution from Broadband Femtosecond Spectroscopies and Calculations

A setup for pump/supercontinuum-probe spectroscopy is described which (i) is optimized to cancel fluctuations of the probe light by single-shot referencing, and (ii) extends the probe range into the near-uv (1000-270 nm). Reflective optics allow 50 μm spot size in the sample and upon entry into two separate spectrographs. The correlation γ(same) between sample and reference readings of probe light level at every pixel exceeds 0.99, compared to γ(consec)<0.92 reported for consecutive referencing. Statistical analysis provides the confidence interval of the induced optical density, ΔOD. For demonstration we first examine a dye (Hoechst 33258) bound in the minor groove of double-stranded DNA. A weak 1.1 ps spectral oscillation in the fluorescence region, assigned to DNA breathing, is shown to be significant. A second example concerns the weak vibrational structure around t=0 which reflects stimulated Raman processes. With 1% fluctuations of probe power, baseline noise for a transient absorption spectrum becomes 25 μOD rms in 1 s at 1 kHz, allowing to record resonance Raman spectra of flavine adenine dinucleotide in the S(0) and S(1) state.

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Femtosecond pump/supercontinuum-probe spectroscopy: optimized setup and signal analysis for single-shot spectral referencing.

In blue-light photoreceptors using flavin (BLUF), the signaling state is formed already within several 100 ps after illumination, with only small changes of the absorption spectrum. The accompanying structural evolution can, in principle, be monitored by femtosecond stimulated Raman spectroscopy (FSRS). The method is used here to characterize the excited-state properties of riboflavin and flavin adenine dinucleotide in polar solvents. Raman modes are observed in the range 90−1800 cm−1 for the electronic ground state S0 and upon excitation to the S1 state, and modes >1000 cm−1 of both states are assigned with the help of quantum-chemical calculations. Line shapes are shown to depend sensitively on resonance conditions. They are affected by wavepacket motion in any of the participating electronic states, resulting in complex amplitude modulation of the stimulated Raman spectra. Wavepackets in S1 can be marked, and thus isolated, by stimulated-emission pumping with the picosecond Raman pulses. Excited-state ...

A. L. Dobryakov

Papers

Femtosecond spectroscopy of condensed phases with chirped supercontinuum probing

Photoisomerization Dynamics and Pathways of trans- and cis-Azobenzene in Solution from Broadband Femtosecond Spectroscopies and Calculations

Femtosecond pump/supercontinuum-probe spectroscopy: optimized setup and signal analysis for single-shot spectral referencing.

Femtosecond Stimulated Raman Spectroscopy of Flavin after Optical Excitation

Evidence for the phantom state in photoinduced cis–trans isomerization of stilbene