Hybrid high spectral resolution broadband mid-infrared SFG spectrometer development and demonstration.

In this work, we present the development of a femtosecond tunable middle infrared (mid-IR) radiation source for the realization of a hybrid concept compact broadband high-resolution sum-frequency generation (SFG) spectroscopy system. For the realization of the new concept, we used a two-channel picosecond fiber laser as a seed for narrowband (∼1.5 cm-1) and broadband ultrafast radiation sources operating at 1 kHz repetition rate. In order to achieve >500 cm-1 bandwidth widely tunable microjoule level pulses in the mid-IR spectral region (2-10 µm), broadband femtosecond source optimization was performed. Numerical simulations with different nonlinear crystals and optical parametric amplification layouts at given fixed initial conditions paved a way to experimentally realize an optimal scheme for a femtosecond mid-IR channel. Fully operating SFG spectrometer setup was assembled and tested. The developed SFG spectrometer demonstrates a unique combination of parameters: excellent spectral resolution (<3 cm-1) similar to a narrowband scanning picosecond spectrometers and fast simultaneous acquisition of broadband spectra up to more than 850 cm-1.

Spectral pulse shaping of a 5 Hz, multi-joule, broadband optical parametric chirped pulse amplification frontend for a 10 PW laser system.

We present a broadband optical parametric chirped pulse amplification (OPCPA) system delivering 4 J pulses at a repetition rate of 5 Hz. It will serve as a frontend for the 1.5 kJ, <150 fs, 10 PW laser beamline currently under development by a consortium of National Energetics and Ekspla. The spectrum of the OPCPA system is precisely controlled by arbitrarily generated waveforms of the pump lasers. To fully exploit the high flexibility of the frontend, we have developed a 1D model of the system and an optimization algorithm that predicts suitable pump waveform settings for a desired output spectrum. The OPCPA system is shown to have high efficiency, a high-quality top-hat beam profile, and an output spectrum demonstrated to be shaped consistently with the theoretical model.

Excitation energy transfer in the LHC-II trimer: from carotenoids to chlorophylls in space and time.

Exciton model for description of experimentally determined excitation energy transfer from carotenoids to chlorophylls in the LHC-II trimer of spinach is presented. Such an approach allows connecting the excitonic states to the spatial structure of the complex and hence descriptions of advancements of the initially created excitations in space and time. Carotenoids were excited at 490 nm and at 500 nm and induced absorbance changes probed in the Chl Q(y) region to provide kinetic data that were interpreted by using the results from exciton calculations. Calculations included the 42 chlorophylls and the 12 carotenoids of the complex, Soret, Q(x) and Q(y) states of the chlorophylls, and the main absorbing S(2) state of the carotenoids. According to the calculations excitation at 500 nm populates mostly a mixed Lut S(2) Chl a Soret state, from where excitation is transferred to the Q(x) and Q(y) states of the Chl a's on the stromal side. Internal conversion of the mixed state to a mixed Lut S(1) and Chl a Q(y) state provides a channel for Lut S(1) to Chl a Q(y) energy transfer. The results from the calculations support a picture where excitation at 490 nm populates primarily a mixed neoxanthin S(2) Chl b Soret state. From this state excitation from neoxanthin is transferred to iso-energetic Chl b Soret states or via internal conversion to S(1) Chl b Q(y) states. From the Soret states excitation proceeds via internal conversion to Q(y) states of Chl b's mostly on the lumenal side. A rapid Chl b to Chl a transfer and subsequent transfer to the stromal side Chl a's and to the final state completes the process after 490 nm excitation. The interpretation is further supported by the fact that excitation energy transfer kinetics after excitation of neoxanthin at 490 nm and the Chl b Q(y) band at 647 nm (Linnanto et al., Photosynth Res 87:267-279, 2006) are very similar.

Ultrafast electronic and vibrational energy relaxation of Fe(acetylacetonate)3 in solution.

Transient mid-infrared spectroscopy is used to probe the dynamics initiated by excitation of ligand-to-metal (400 nm) and metal-to-ligand (345 nm) charge transfer states of FeIII complexed with acetylacetonate (Fe(acac)3, where acac stands for deprotonated anion of acetylacetone) in solution. Transient spectra in the 1500-1600 cm-1 range show two broad absorptions red-shifted from the bleach of the nu(CO) (approximately 1575 cm-1) and nu(C=C) (approximately 1525 cm-1) ground state absorptions. Bleach recovery kinetics has a time constant of 12-19 ps in chloroform and tetrachloroethylene and it decreases by 30-40% in a 10% mixture of methanol in tetrachloroethylene. The transient absorptions experience band narrowing simultaneously with blue-shifting of the absorption maxima. Both phenomena have time constants of 3-9 ps with no evident dependence on the solvent. The experimental observations are ascribed to fast conversion of the initially excited charge transfer states to the ligand field manifold, and subsequent vibrational cooling on the lowest ligand field excited state prior to electronic conversion to the ground state. The analysis of time dependent bandwidths and positions of the transient absorptions provides some evidence of mode specific vibrational cooling.

Excitation energy transfer in the LHC-II trimer: a model based on the new 2.72 A structure.

Energy transfer of the light harvesting complex LHC-II trimer, extracted from spinach, was studied in the Q(y) region at room temperature by femtosecond transient absorption spectroscopy. Configuration interaction exciton method [Linnanto et al. (1999) J Phys Chem B 103: 8739-8750] and 2.72 A structural information reported by Liu et al. was used to calculate spectroscopic properties and excitation energy transfer rates of the complex. Site energies of the pigments and coupling constants of pigment pairs in close contact were calculated by using a quantum chemical configuration interaction method. Gaussian random variation of the diagonal and off-diagonal exciton matrix elements was used to account for inhomogeneous broadening. Rate calculations included only the excitonic states initially excited and probed in the experiments. A kinetic model was used to simulate time and wavelength dependent absorption changes after excitation on the blue side of the Q(y) transition and compared to experimentally recorded rates. Analysis of excitonic wavefunctions allowed identification of pigments initially excited and probed into later. It was shown that excitation of the blue side of the Q(y) band of a single LHC-II complex results in energy transfer from chlorophyll b's of the lumenal side to chlorophyll a's located primarly on one of the monomers of the stromal side.