Time- and Angle-Resolved Photoemission Spectroscopy of Hydrated Electrons Near a Liquid Water Surface

世界で初めて、溶液反応の超高速時間・角度分解光電子分光に成功 --溶液化学反応の機構解明に前進--. 京都大学プレスリリース. 2014-04-22.We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1, 4-diazabicyclo[2, 2, 2]octane and I− in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed

Time-resolved photoelectron spectroscopy of bulk liquids at ultra-low kinetic energy

Time-resolved photoelectron spectroscopy (TR-PES) of ultrafast dynamics in solution is presented. To measure the photoelectron kinetic energy distribution (PKED) that is free from inelastic scattering in solution, photoelectrons were generated with ultra-low kinetic energies (ULKE: <5 eV). Time constants of the elementary processes in the charge-transfer-to-solvent (CTTS) reaction from I− to bulk water were in excellent agreement with those obtained by transient absorption spectroscopy, demonstrating the bulk-sensitivity of TR-PES-ULKE. The analysis suggests that the CTTS reaction proceeds via two intermediates, and that 30% of the first intermediate and 70% of the second intermediate respectively are quenched by geminate recombination between the electron and the neutral iodine atom

Charge Transfer Reactions from I⁻ to Polar Protic Solvents Studied Using Ultrafast Extreme Ultraviolet Photoelectron Spectroscopy

Charge transfer reactions from I– to solvent water, methanol, and ethanol were studied using extreme ultraviolet time-resolved photoelectron spectroscopy (EUV-TRPES). This technique eliminates spectral broadening, previously seen in UV-TRPES, caused by electron inelastic scattering in liquids, and enables clear observation of the temporal evolution of the spectral shape. The peak position, width, and intensity of the electron binding energy distribution indicate electron detachment and subsequent solvation and thermalization processes. Geminate recombination between detached electrons and iodine atoms is discussed using a diffusion equation and a global fitting analysis based on a kinetics model

Ultrafast photodynamics of pyrazine in the vacuum ultraviolet region studied by time-resolved photoelectron imaging using 7.8-eV pulses

The ultrafast electronic dynamics of pyrazine (C4N2H4) were studied by time-resolved photoelectron imaging (TRPEI) using the third (3ω, 4.7 eV) and fifth harmonics (5ω, 7.8 eV) of a femtosecond Ti:sapphire laser (ω). Although the photoionization signals due to the 5ω - 3ω and 3ω - 5ω pulse sequences overlapped near the time origin, we have successfully extracted their individual TRPEI signals using least squares fitting of the observed electron kinetic energy distributions. When the 5ω pulses preceded the 3ω pulses, the 5ω pulses predominantly excited the S4 (ππ∗, 1B1 u+1B2u) state. The photoionization signal from the S4 state generated by the time-delayed 3ω pulses was dominated by the D3(2B2g)←S4 photoionization process and exhibited a broad electron kinetic energy distribution, which rapidly downshifted in energy within 100 fs. Also observed were the photoionization signals for the 3s, 3pz, and 3py members of the Rydberg series converging to D0(2Ag). The Rydberg signals appeared immediately within our instrumental time resolution of 27 fs, indicating that these states are directly photoexcited from the ground state or populated from S4 within 27 fs. The 3s, 3pz, and 3py states exhibited single exponential decay with lifetimes of 94 ± 2, 89 ± 2, and 58 ± 1 fs, respectively. With the reverse pulse sequence of 3ω - 5ω, the ultrafast internal conversion (IC) from S2(ππ∗) to S1(nπ∗) was observed. The decay associated spectrum of S2 exhibited multiple bands ascribed to D0, D1, and D3, in agreement with the 3ω-pump and 6ω-probe experiment described in our preceding paper [T. Horio et al., J. Chem. Phys. 145, 044306 (2016)]. The electron kinetic energy and angular distributions from S1 populated by IC from S2 are also discussed

Theory of time-resolved photoelectron imaging: nonperturbative calculation for an internally converting polyatomic molecule

We present the first calculation of time-resolved photoelectron angular distributions for a polyatomic system. Our method takes rotations into exact account, treats the laser field nonperturbatively, and computes the electronic dynamics from first principles. Our results point to the information content of time-resolved photoelectron imaging observables and illustrate the role played by the field intensity.NRC publication: Ye

Charge-transfer-to-solvent reactions from I- to water, methanol, and ethanol studied by time-resolved photoelectron spectroscopy of liquids

The charge-transfer-to-solvent (CTTS) reactions from iodide (I-) to H2O, D2O, methanol, and ethanol were studied by time-resolved photoelectron spectroscopy of liquid microjets using a magnetic bottle time-of-flight spectrometer with variable pass energy. Photoexcited iodide dissociates into a weak complex (a contact pair) of a solvated electron and an iodine atom in similar reaction times, 0.3 ps in H2O and D2O and 0.5 ps in methanol and ethanol, which are much shorter than their dielectric relaxation times. The results indicate that solvated electrons are formed with minimal solvent reorganization in the long-range solvent polarization field created for I-. The photoelectron spectra for CTTS in H2O and D2O - measured with higher accuracy than in our previous study [Y. I. Suzuki et al., Chem. Sci. 2, 1094 (2011)] - indicate that internal conversion yields from the photoexcited I-star (CTTS) state are less than 10%, while alcohols provide 2-3 times greater yields of internal conversion from I-star. The overall geminate recombination yields are found to be in the order of H2O > D2O > methanol > ethanol, which is opposite to the order of the mutual diffusion rates of an iodine atom and a solvated electron. This result is consistent with the transition state theory for an adiabatic outer-sphere electron transfer process, which predicts that the recombination reaction rate has a pre-exponential factor inversely proportional to a longitudinal solvent relaxation time

Charge Transfer Reactions from I⁻ to Polar Protic Solvents Studied Using Ultrafast Extreme Ultraviolet Photoelectron Spectroscopy

Charge transfer reactions from I– to solvent water, methanol, and ethanol were studied using extreme ultraviolet time-resolved photoelectron spectroscopy (EUV-TRPES). This technique eliminates spectral broadening, previously seen in UV-TRPES, caused by electron inelastic scattering in liquids, and enables clear observation of the temporal evolution of the spectral shape. The peak position, width, and intensity of the electron binding energy distribution indicate electron detachment and subsequent solvation and thermalization processes. Geminate recombination between detached electrons and iodine atoms is discussed using a diffusion equation and a global fitting analysis based on a kinetics model

Full observation of ultrafast cascaded radiationless transitions from S2(ππ-) state of pyrazine using vacuum ultraviolet photoelectron imaging

A photoexcited molecule undergoes multiple deactivation and reaction processes simultaneously or sequentially, which have been observed by combinations of various experimental methods. However, a single experimental method that enables complete observation of the photo-induced dynamics would be of great assistance for such studies. Here we report a full observation of cascaded electronic dephasing from S2(ππ∗) in pyrazine (C4N2H4) by time-resolved photoelectron imaging (TRPEI) using 9.3-eV vacuum ultraviolet pulses with a sub-20 fs time duration. While we previously demonstrated a real-time observation of the ultrafast S2(ππ∗) → S1(nπ∗) internal conversion in pyrazine using TRPEI with UV pulses, this study presents a complete observation of the dynamics including radiationless transitions from S1 to S0 (internal conversion) and T1(nπ∗) (intersystem crossing). Also discussed are the role of 1Au(nπ∗) in the internal conversion and the configuration interaction of the S2(ππ∗) electronic wave function