Photoexcitation

About: Photoexcitation is a research topic. Over the lifetime, 5874 publications have been published within this topic receiving 134733 citations.

Ultraviolet photochemical reaction of [Fe(III)(C2O4)3]3− in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser

Abstract: Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III) oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3 eV and 200 fs, respectively. A femtosecond 268 nm pulse was employed to excite [Fe(III)(C2O4)3](3-) in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s), and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268 nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4 eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III)(C2O4)3](3-). The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III) is upon excitation immediately photoreduced to Fe(II), followed by ligand dissociation from Fe(II). Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO2 (•))Fe(II)(C2O4)2](3-) and subsequently [Fe(II)(C2O4)2](2-).

Tunneling in jet-cooled 5-methyltropolone and 5-methyltropolone-od. coupling between internal rotation of methyl group and proton transfer

Abstract: The coupling of two large amplitude motions, the internal rotation of the methyl group and the intramolecular proton transfer, has been investigated for jet-cooled 5-methyltropolone, 5-methyltropolone–OD, and the 5-methyltropolone–(H2O)1 1:1 hydrogen-bonded complex by measuring the fluorescence excitation, dispersed fluorescence, and hole-burning spectra in the S1–S0 region. The vibronic bands in the excitation spectrum of 5-methyltropolone consist of four components originating from the transitions between the sublevels in the S1 and S0 states. The intensity of the bands, the frequencies, and the change in the stable conformation of the methyl group upon photoexcitation have been analyzed for 5-methyltropolone–(H2O)1 by calculating the one-dimensional periodic potential function, which provides the correlation between the internal rotational levels of 5-methyltropolone–(H2O)1 and the sublevels of 5-methyltropolone. It has been shown that the electronic transitions between the sublevels within the same sy...

Absorption spectrum of C60 in the gas phase: Autoionization via core‐excited Rydberg states

Abstract: The absolute absorption cross section of C60 in the gas phase (830–870 K) was measured as a function of the photon energy (3.5–11.4 eV) (absorption spectrum). Absorption peaks at 7.87, 8.12, 8.29, 9.2 eV and a dip at 8.45 eV observed are assigned as Feshbach resonances in the photoexcitation involving superexcited states. The superexcited states responsible for the 7.87, 8.12, and 9.2 eV peaks are assigned to be core‐excited Rydberg states converging to the second, the third and the fourth ionization limits of C60 (8.89, 9.12, 10.82–11.59 eV), respectively. The 8.29 eV peak is considered to originate from vibrational excitation of a totally symmetric pentagonal pinch mode of the superexcited state responsible for the 8.12 eV peak. Further, a relative photoionization quantum yield was estimated from the absorption cross section measured and the relative photoionization cross section reported. The yield increases particularly in the vicinity of 8 eV in accordance with a high efficiency of autoionization of ...

Three and four-photon absorption of a multiphoton absorbing fluorescent probe

Abstract: The utility of multiphoton excitation processes has been the subject of increased attention due to their potential applications in biophotonics, biology, and medicine through three-dimensional fluorescence imaging and photodynamic therapy. Evidence of this are the multiple applications of two-photon absorption (2PA) in fluorescence spectroscopy and 3D imaging over the last several years because of its large effective Stoke?s Shift and high spatial resolution.[l,2] However, because the irradiation penetration depth of 2PA is limited in medical and biological applications due to the unwanted absorption and scattering when two red photons are used, the scientific communib recently started to explore higher order absorption processes at longer wavelengths such as three- (3PA) and four-photon absorption (IPA) that minimize the scattered light losses, and reduce the unwanted linear absorption in the living organism transparency window.