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A home-built cavity-dumped chromium:forsterite laser was used as light source for the development of the femtosecond near-infrared laser microscope to detect the multiphoton fluorescence of organic microcrystals. The application of this system explained the association of simultaneous three- and four-photon absorption processes with the production of the excited state for perylene and anthracene microcrystals, respectively.

Vibrational coherence in the degenerate four-wave-mixing (DFWM) signal generated from polymer films doped with a dye, oxazine at 10 K was investigated. It was revealed that low-frequency oscillations with weak coupling to the optical transition can be enhanced in the stimulated photon echo signal compared to the transient grating signal.

Femtosecond time-resolved transient absorption spectroscopy was performed for a nonfluorescent solvatochromic dye, phenol blue, N -(4-dimethylaminophenyl)-1,4-benzoquinoneimine, which exhibits ultrafast nonradiative decay due to its flexible molecular structure. By exciting the molecule in ethanol (EtOH) solution with two excitation wavelengths located at shorter- and longer-wavelength sides of the visible absorption band, we observed ultrafast nonradiative decay from the excited state, followed by spectral evolution in the ground state. The nonradiative decay in the subpicosecond range creates a vibrationally hot ground state with the lifetime in the picosecond range. Subsequently, a tautomer that absorbs at shorter wavelengths is produced from the hot state, which causes a red shift of the ground-state bleach (GSB). The tautomerization presumably involves twisting of the benzoquinoneimine moiety induced by the breaking of the hydrogen bond (H-bond) between the solute and the solvent molecules. The recombination of the H-bond occurs with a time constant of ∼30 ps, and the system returns to its original state. We also observed low-frequency coherent wavepacket oscillations that modulate the GSB with dephasing times similar to the excited-state lifetime.

Ultrafast excited-state dynamics of CuBr 3 - complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr 3 - complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr 3 - complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr 3 - complex exists as [CuBr 3 (CH 3 CN) 2 ] - , whereas three forms of this complex, [CuBr 3 CH 2 Cl 2 ] - , [CuBr 3 (CH 2 Cl 2 ) 2 ] - , and [CuBr 3 (CH 2 Cl 2 ) 3 ] - , are present in equilibrium in dichloromethane.

Excitation energy transfer (EET) in light-harvesting proteins is vital for photosynthetic activities. The pigment compositions and their organizations in these proteins are responsible for the EET functions. Thus, changing the pigment compositions in light-harvesting proteins contributes to a better understanding of EET mechanisms. In this study, we investigated the EET dynamics of two light-harvesting complex 2 (LH2) variants, in which nine B800 bacteriochlorophyll (BChl) a pigments were entirely or half converted to 3-acetyl chlorophyll (AcChl) a . The AcChl a pigments showed a Q y band, which was blue-shifted by 107 nm from B800 BChl a in the two variants. EET from AcChl a to B850 BChl a was observed in both fully oxidized and half-oxidized LH2 variants, but the EET rates were lower than that from B800 to B850 BChl a . EET from AcChl a to the co-present B800 was barely detected in the half-oxidized LH2. The preferential EET from AcChl a to B850 instead of B800 was rationalized by little spectral overlap of AcChl a with B800 BChl a and the pigment geometry in the protein. The EET rate from B800 to B850 BChl a in the half-oxidized LH2 was analogous to that in native LH2, indicating that partial oxidation of B800 did not disturb the EET channel from the residual B800 to B850.

Control of the spectral overlap between energy donors and acceptors provides insight into excitation energy transfer (EET) mechanisms in photosynthetic light-harvesting proteins. Substitution of energy-donating B800 bacteriochlorophyll (BChl) a with other pigments in the light-harvesting complex 2 (LH2) of purple photosynthetic bacteria has been extensively performed; however, most studies on the B800 substitution have focused on the decrease in the spectral overlap integral with energy-accepting B850 BChl a by reconstitution of chlorophylls into the B800 site. Here, we reconstitute BChl b into the B800 site of the LH2 protein from Rhodoblastus acidophilus to increase the spectral overlap with B850 BChl a . BChl b in the B800 site had essentially the same hydrogen-bonding pattern as B800 BChl a , whereas it showed a red-shifted Q y absorption band at 831 nm. The EET rate from BChl b to B850 BChl a in the reconstituted LH2 was similar to that of native LH2 despite the red shift of the Q y band of the energy donor. These results demonstrate the importance of the contribution of the density of excitation states of the B850 circular assembly, which incorporates higher lying optically forbidden states, to intracomplex EET in LH2.

Femtosecond near-infrared laser microscope was developed with a home-built cavity-dumped chromium:forsterite laser as a light source centered at 1.26 microm. Optimization of the pulse duration achieved 35 fs fwhm at the sample position of the microscope after passing through a 100x objective. This system was applied to the detection of multiphoton fluorescence of some organic microcrystals. Excitation intensity dependence and the interferometric autocorrelation detection of the fluorescence clearly demonstrated that simultaneous three- and four-photon absorption processes are responsible for the production of the excited state for perylene and anthracene microcrystals, respectively. The spatial resolution along the optical axis and its dependence on the order of the multiphoton process were also discussed.