The energy level structure and dynamics of biomolecules are important for understanding their photoinduced function. In particular, the role of carotenoids in light-harvesting is heavily studied, yet not fully understood. The conventional approach to investigate these processes involves analysis of the third-order optical polarization in one spectral dimension. Here, we record two-dimensional correlation spectra for different time-orderings to characterize all components of the transient molecular polarization and the optical signal. Single- and double-quantum two-dimensional experiments provide insight into the energy level structure as well as the ultrafast dynamics of solvated β-carotene. By analysis of the lineshapes, we obtain the transition energy and characterize the potential energy surfaces of the involved states. We obtain direct experimental proof for an excited state absorption transition in the visible (S2→Sn2). The signatures of this transition in pump-probe transients are shown to lead to strongly damped oscillations with characteristic pump and probe frequency dependence.
For benzhydryl chloride compounds we observe that photodissociation only leads to radical pairs. The typically observed cations are formed by subsequent electron transfer. Reactions of cations in neat alcohols can then occur within 2.6 ps.
The bandwidth of ultrafast pulses in the UV is limited by the finite acceptance bandwidth of the nonlinear crystals used for their generation. For fundamental laser pulses it is well established that spectral broadening can be used to overcome intrinsic bandwidth limits. We show that self-phase modulation of UV pulses in bulk materials leads to large spectral broadening and allows for a significant reduction of the pulse duration. We find that for pulse energies in the range of a few μJ, a thin crystal is favorable due to the strong dispersion in the UV and the limitations set by self-focusing. In contrast to spectral broadening in gaseous media, the self-focus has to lie outside the crystal to avoid beam break up. We focus UV pulses into a 1 mm thick CaF2 crystal. For moderately short input pulses, a shortening factor up to 2.4 is achieved: the 120 fs long third harmonic output of a Ti:sapphire amplifier is compressed down to 50 fs FWHM. For a central wavelength of 315 nm, we generate pulses as short as 14.9 fs after compression with an UV pulse shaper. In both cases the resulting beam shape is close to Gaussian and fully usable for spectroscopic experiments. We use the pulses in a collinear 2D-UV experiment and clearly resolve vibronic off-diagonal peaks of the S2 1B2u vibronic progression of pyrene.
The interaction of exciton and charge transfer (CT) states plays a central role in photo-induced CT processes in chemistry, biology and physics. In this work, we use a combination of two-dimensional electronic spectroscopy (2D-ES), pump-probe measurements and quantum chemistry to investigate the ultrafast CT dynamics in a lutetium bisphthalocyanine dimer in different oxidation states. It is found that in the anionic form, the combination of strong CT-exciton interaction and electronic asymmetry induced by a counter-ion enables CT between the two macrocycles of the complex on a 30 fs timescale. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra, and we monitor how the excited state charge density ultimately localizes on the macrocycle closest to the counter-ion within 100 fs. A comparison with the dynamics in the radical species further elucidates how CT states modulate the electronic structure and tune fs-reaction dynamics. Our experiments demonstrate the unique capability of 2D-ES in combination with other methods to decipher ultrafast CT dynamics.
Experimental realizations of two-dimensional (2D) electronic spectroscopy in the ultraviolet (UV) must so far contend with a limited bandwidth in both the excitation and particularly the probe frequency. The pump bandwidth is at best 1500 cm−1 (full width at half maximum) at a fixed wavelength of 267 nm or 400 cm−1 for tunable pulses. The use of a replica of the pump pulse as a probe limits the observation of photochemical processes to the excitation region and makes the disentanglement of overlapping signal contributions difficult. We show that 2D Fourier transform spectroscopy can be conducted in a shaper-assisted collinear setup comprising fully tunable UV pulse pairs and supercontinuum probe spanning 250–720 nm. The pump pulses are broadened up to a useable spectral coverage of 2000 cm−1 (25 nm at 316 nm) by self-phase modulation in bulk CaF2 and compressed to 18 fs. By referencing the white light probe and eliminating pump stray light contributions, high signal-to-noise ratios even for weak probe intensities are achieved. Data acquisition times as short as 4 min for a selected population time allow the rapid recording of 2D spectra for photolabile biological samples even with the employed 1 kHz laser system. The potential of the setup is demonstrated on two representative molecules: pyrene and 2,2-diphenyl-5,6-benzo(2H)chromene. Well-resolved cross-peaks are observed and the excitation energy dependence of the relaxation processes is revealed.
Pump–probe spectroscopy, time resolved fluorescence, chemical variation and quantum chemical calculations reveal an efficient energy transfer mechanism enabled by a bright charge transfer state located on the spacer.
A combination of experimental and theoretical techniques is used to study the photoinduced ring-opening/closure of a trifluoromethyl-indolylfulgide. Time-resolved UV/vis pump and IR probe measurements are performed in the subpicosecond to 50 ps time range. Probing in the mid-IR between 1200 and 1900 cm(-1) provides mode-specific dynamics and reveals photochemical reaction dynamics as well as the presence of a noncyclizable conformer. Ring-opening occurs with about 3 ps. Experiments on the open isomer confirm that the ring-closure occurs on the subpicosecond time scale. They also show a 10 ps transient that can be assigned to internal conversion of a noncyclizable conformer. Quantum chemical calculations with multireference methods are used to explore the complex potential energy landscape in the excited electronic state showing paths for ring-opening and closure reactions as well as for competing side-reactions. The calculations reveal that photoexcitation induces a charge transfer from the indole to the anhydride. The same charge transfer drives the system toward a low-energy conical intersection seam spreading from the closed to the open ring side and is responsible for the ultrafast relaxation to the ground state. The ultrafast photoreactivity comes at the expense of selectivity.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Complex multi-stage relaxation and reaction pathways after the optical excitation of molecules makes the disentanglement of the underlying mechanisms challenging. We present four examples that a new transient spectrometer with excitation fully tunable from the deep UV to the IR and 225 to 1700 nm probing allows for an analysis with greatly reduced ambiguity. The temporal resolution of about 50 fs allows us to resolve all relevant processes. For each example there is a new twist in the sequence of relaxation steps that had previously been overlooked. In malachite green it appears that the importance of the phenyl twisting has been overemphasized and rather a charge transfer state should be considered. In TINUVIN-P the predicted twisting as the driving motion for the ultrafast IC is confirmed and leads to a resolution of the earlier puzzle that the sub-5 ps regime shows kinetics deviating from a pure cooling process despite the sub-ps proton transfer cycle. For the bond cleavage of Ph2CH-Cl and Ph2CH-Br the degree of electron transfer within the radical pair can now be determined quantitatively and leads to a profound understanding of the long-term cation yield. For the first time coherent wavepacket motion in the photoproducts is reported. Last but not least the measurement of the GSB recovery in the deep UV allows for the surprising result, that even after S2 excitation of cyclopentenones the triplet states are reached with near unity probability within a few picoseconds.
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