Resolving Nonadiabatic Dynamics of Hydrated Electrons Using Ultrafast Photoemission Anisotropy

Karashima, Shutaro; Yamamoto, Yasumichi; Suzuki, Toshinori

doi:10.1103/physrevlett.116.137601

Cited by 34 publications

(95 citation statements)

References 24 publications

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“…Substantial progress has been made in recent years regarding its structural and electronic properties ( 5 – 21 ) and the excited-state relaxation dynamics over a broad time window, ranging from femtoseconds to beyond picoseconds ( 9 , 10 , 13 , 22 – 32 ). The most controversial issues concern the ground-state structure (cavity-forming versus non–cavity-forming), the relaxation mechanisms from electronically excited states (adiabatic versus nonadiabatic), the existence of a long-lived surface electron, accurate values for electron binding energies (eBE), and the influence of electron scattering.…”

Section: Introductionmentioning

confidence: 99%

“…Without detailed scattering parameters and simulations, the actual effect of scattering remained unclear so that no genuine VBE (g) could be extracted from the experimental spectra. Similarly, the importance of electron scattering for the interpretation of experimental PADs was recognized ( 22 , 23 , 34 , 45 ), but without accurate scattering simulations, its quantification remained elusive. PADs are very sensitive to the actual values of the scattering cross sections.…”

Section: Introductionmentioning

confidence: 99%

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Genuine binding energy of the hydrated electron

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Genuine binding energy of the hydrated electron

et al. 2017

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“…Last, the study of water clusters carrying an excess electron (2,(17)(18)(19)(20)(21) or deposited alkali atoms (22) has also provided valuable insights into the hydrated electron. Despite some controversies, e.g., concerning the binding motif of the electron or energy extrapolation from water clusters to bulk water (9,10,12,15,19,20,22,23), the thermalized hydrated electron is now well characterized experimentally (22)(23)(24)(25)(26)(27).…”

Section: Introductionmentioning

confidence: 99%

Real-time observation of water radiolysis and hydrated electron formation induced by extreme-ultraviolet pulses

et al. 2020

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The dominant pathway of radiation damage begins with the ionization of water. Thus far, however, the underlying primary processes could not be conclusively elucidated. Here, we directly study the earliest steps of extreme ultraviolet (XUV)–induced water radiolysis through one-photon excitation of large water clusters using time-resolved photoelectron imaging. Results are presented for H2O and D2O clusters using femtosecond pump pulses centered at 133 or 80 nm. In both excitation schemes, hydrogen or proton transfer is observed to yield a prehydrated electron within 30 to 60 fs, followed by its solvation in 0.3 to 1.0 ps and its decay through geminate recombination on a ∼10-ps time scale. These results are interpreted by comparison with detailed multiconfigurational non-adiabatic ab-initio molecular dynamics calculations. Our results provide the first comprehensive picture of the primary steps of radiation chemistry and radiation damage and demonstrate new approaches for their study with unprecedented time resolution.

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“…elastic and inelastic scattering during electron transport in the liquid. We treat this effect within the detailed scattering model mentioned above (section S3 in [22] and [7,9,10]) to simulate a typical liquid microjet experiment [12][13][14][16][17][18], illustrated in Fig. S5 [22], where illustrates the pronounced effect of contribution (iv) on the PADs of the liquid, viz.…”

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confidence: 99%

“…As the photoelectron angular distribution (PAD) is particularly sensitive to electron scattering it has recently received increasing attention in this context [7,10,[13][14][15][16][17][18]. It is often described by a single anisotropy parameter β, defined by Eq.…”

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Size-Resolved Photoelectron Anisotropy of Gas Phase Water Clusters and Predictions for Liquid Water

et al. 2017

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We report the first measurement of size-resolved photoelectron angular distributions for the valence orbitals of water clusters with up to 20 molecules. A systematic decrease of the photoelectron anisotropy is found for clusters with up to 5-6 molecules, and most remarkably, convergence of the anisotropy for larger clusters. We suggest the latter to be the result of a local short-range scattering potential that is fully described by a unit of 5-6 molecules. The cluster data and a detailed electron scattering model are used to predict liquid water anisotropies. Reasonable agreement with experimental liquid jet data is found.A detailed understanding of elastic and inelastic scattering of electrons in liquid water is of fundamental importance for the modelling of radiation damage in biological systems, the description of the behaviour of the solvated electron in chemistry, and for the quantitative interpretation of photoelectron spectra of liquid water and aqueous solutions [1][2][3][4][5][6][7][8]. For slow electrons (electron kinetic energy eKE ≲ 50 eV), detailed experimental scattering parameters (differential scattering cross sections and energy losses) were so far only reported for amorphous ice [9]; with the exception of very slow electrons (eKE ≲ 6 eV), for which liquid water data were recently obtained from photoelectron velocity map imaging (VMI) of liquid water droplets [10]. Since there is little reason to expect substantial differences between amorphous ice and liquid water for electronic scattering processes (eKEs ≳ 6 eV) the amorphous ice and liquid droplet data [9,10] should now provide a reasonable data set for scattering simulations of liquid water. In addition, electron attenuation lengths (EALs) for eKEs ≳ 3 eV are available for liquid water from various microjet studies [11-13], which, however, do not allow quantitative predictions of the scattering contributions.The photoelectron angular distribution (PAD) is particularly sensitive to electron scattering and has thus recently received increasing attention in this context [7,10,[13][14][15][16][17][18]. Often, the information in the PAD is described by a single anisotropy parameter β (see Eq. ( 1)). For the liquid microjet, this is an approximation which we also follow in the present work. For ionization from the O1s orbital of liquid water, Thürmer et al. observed a more isotropic PAD; i. e. a smaller β-value; for liquid water compared with gas phase water over the eKE range from ~12 -450 eV [13]. For core-level ionization, this reduction is assumed to mainly arise from electron scattering within the liquid. For the ionization from the valence orbitals 1b 1 , 3a 1 , and 1b 2 , additional changes in the initial state due to orbital mixing also mediated by hydrogen-bonding are expected to contribute to the difference in β-values between gas and liquid phase. While monomer gas phase β-parameters have been reported for the three valence orbitals at photon energies 18 eV ≤ hν < 139 eV [15,16,[19][20][21], corresponding values for liquid water have t...

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Resolving Nonadiabatic Dynamics of Hydrated Electrons Using Ultrafast Photoemission Anisotropy

Cited by 34 publications

References 24 publications

Genuine binding energy of the hydrated electron

Genuine binding energy of the hydrated electron

Real-time observation of water radiolysis and hydrated electron formation induced by extreme-ultraviolet pulses

Size-Resolved Photoelectron Anisotropy of Gas Phase Water Clusters and Predictions for Liquid Water

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