Excitation energy dependence of the photoionization of liquid water

Sander, M.; Luther, K.; Troe, J.

doi:10.1021/j100146a023

Cited by 90 publications

(134 citation statements)

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“…We adjust the spot size and pulse energy of the pump beam in order to eliminate transient absorption contributions from the products of two-͑pump͒-photon ionization of water. [13][14][15]28 The spot size of the pump beam is at least twice that of the probe, and the pump pulse energy is between 0.8 and 6.6 J. The 2PA spectrum is obtained for parallel and perpendicular polarization by rotating the linear polarization axis of the 800 nm beam prior to continuum generation.…”

Section: A Experimental Methodsmentioning

confidence: 99%

“…The discrepancy indicates that multiple transitions contribute to the spectrum in this energy range, and highlights how little is known about the character of the excited states for oneand 2PA of liquid water. [13][14][15] FIG…”

Section: A Two-photon Absorption Spectrummentioning

confidence: 99%

“…Specifically, we report the continuous 2PA spectrum of water in the range from 7 to 10 eV and use the polarization dependence of the spectrum to assign valence transitions in greater detail than was previously possible. Better knowledge of the electronic structure helps explain the unique ionization properties of liquid water, [13][14][15] which has a vertical ionization potential of 11 eV, but can be ionized adiabatically down to the optical absorption edge near 6-6.5 eV. 16,17 One-photon absorption ͑1PA͒ spectroscopy of the isolated water molecule, for which hydrogen-bonding effects are absent, provides an important reference point for understanding the liquid spectrum.…”

Section: Introductionmentioning

confidence: 99%

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Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Elles¹,

Rivera²,

Zhang³

et al. 2009

The Journal of Chemical Physics

106

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Two-photon absorption ͑2PA͒ spectroscopy in the range from 7 to 10 eV provides new insight on the electronic structure of liquid water. Continuous 2PA spectra are obtained via the pump-probe technique, using broadband probe pulses to record the absorption at many wavelengths simultaneously. A preresonance enhancement of the absolute 2PA cross section is observed when the pump-photon energy increases from 4.6 to 6.2 eV. The absorption cross section also depends on the relative polarization of the pump and probe photons. The variation of the polarization ratio across the spectrum reveals a detailed picture of the 2PA and indicates that at least four different transitions play a role below 10 eV. Theoretical polarization ratios for the isolated molecule illustrate the value of the experimental polarization measurement in deciphering the 2PA spectrum and provide the framework for a simple simulation of the liquid spectrum. A more comprehensive model goes beyond the isolated molecule picture and connects the 2PA spectrum with previous one-photon absorption, photoelectron, and x-ray absorption spectroscopy measurements of liquid water. Previously unresolved, overlapping transitions are assigned for the first time. Finally, the electronic character of the vertical excited states is related to the energy-dependent ionization mechanism of liquid water.

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Section: A Experimental Methodsmentioning

confidence: 99%

Section: A Two-photon Absorption Spectrummentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Elles¹,

Rivera²,

Zhang³

et al. 2009

The Journal of Chemical Physics

106

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“…In order to facilitate a comparison of our results with those in the literature, we include only data points obtained from the IRT/IP model. The most common alternative in the literature is a simple survival probability model that takes the form of the complementary error function, 14,32 and it essentially approximates the geminate kinetics of the electron as a single diffusion-limited recombination reaction with a ␦-function initial distribution. The simple model tends to overestimate the survival probability, because it generally fits the data poorly at short delay times, and does not provide a quantitative estimate of the electron ejection length.…”

Section: ͑5͒mentioning

confidence: 99%

“…13 Other experiments at excitation energies up to 10 eV support the observation that the ejection length increases rapidly above 9 -9.5 eV, 6,14-21 although there are substantial difficulties in comparing previous results due to different methods of reporting recombination yields and the use of different fitting procedures. Further complicating that comparison is the fact that only a few authors specifically examine the energy dependence of the ionization mechanism over a broad range of energies, 6,8,12,14,15,22 and that, with the exception of a recent study at 12.4 eV by one of our groups, 21 there are no reliable data for excitation energies above 10 eV.…”

Section: Introductionmentioning

confidence: 99%

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Elles

Jailaubekov

Crowell

et al. 2006

The Journal of Chemical Physics

122

192

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Transient absorption measurements monitor the geminate recombination kinetics of solvated electrons following two-photon ionization of liquid water at several excitation energies in the range from 8.3 to 12.4 eV. Modeling the kinetics of the electron reveals its average ejection length from the hydronium ion and hydroxyl radical counterparts and thus provides insight into the ionization mechanism. The electron ejection length increases monotonically from roughly 0.9 nm at 8.3 eV to nearly 4 nm at 12.4 eV, with the increase taking place most rapidly above 9.5 eV. We connect our results with recent advances in the understanding of the electronic structure of liquid water and discuss the nature of the ionization mechanism as a function of excitation energy. The isotope dependence of the electron ejection length provides additional information about the ionization mechanism. The electron ejection length has a similar energy dependence for two-photon ionization of liquid D 2 O, but is consistently shorter than in H 2 O by about 0.3 nm across the wide range of excitation energies studied.

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Comments on time‐resolved charge transfer with hot electrons at the silver/electrolyte interface

Kulmala

Ala-Kleme

1997

Ber Bunsenges Phys Chem

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Additional information is presented to that previously published by Diesing et al. in this journal considering metal/insulator/meta1 tunnel junctions in contact with aqueous solution. Hot electron injection into aqueous electrolyte solutions from metal/insulator/metal/electrolyte and metal/insulator/electrolyte tunnel junctions is considered and the thermodynamic basis of probable electrochemical generation of hydrated electrons is discussed.

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Excitation energy dependence of the photoionization of liquid water

Cited by 90 publications

References 4 publications

Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Comments on time‐resolved charge transfer with hot electrons at the silver/electrolyte interface

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