Direct observation of the absorption bands of the first electronic transition in liquid H2O and D2O by attenuated total reflectance far-UV spectroscopy

Ikehata, Akifumi; Higashi, Noboru; Ozaki, Yukihiro

doi:10.1063/1.3039080

Cited by 78 publications

(117 citation statements)

References 40 publications

(52 reference statements)

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“…We attribute these differences to the necessary Kramers-Kronig transformations and analysis inherent to these other studies, whereas our transmission measurement is direct. The entire spectrum redshifts linearly with increasing temperature, in agreement with previous predictions 14,15,[30][31][32] , and by 350°C it has shifted by 0.64 eV to lower energy compared to room temperature. The energy of maximum absorbance, E max , steadily decreases by -0.00203 eV°C À 1 (16.4 cm À 1°C À 1 ) ( Supplementary Fig.…”

Section: Resultssupporting

confidence: 78%

“…The energy of maximum absorbance, E max , steadily decreases by -0.00203 eV°C À 1 (16.4 cm À 1°C À 1 ) ( Supplementary Fig. 1), also in reasonable agreement with previous experimental approximations 14,15,34 and theoretical predictions 21 . The maximum extinction coefficient steadily decreases linearly (e max ¼ À 0.965T þ 1,598) with increasing temperature, and by 350°C reaches B80% of its roomtemperature value (Supplementary Fig.…”

Section: Resultssupporting

confidence: 75%

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Vacuum Ultraviolet Spectroscopy of the Lowest-Lying Electronic State in Sub-Critical and Supercritical Water

Marin¹,

Bartels²,

Janik³

2016

Proceedings of the 71st International Symposium on Molecular Spectroscopy

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The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

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Section: Resultssupporting

confidence: 78%

Section: Resultssupporting

confidence: 75%

Vacuum Ultraviolet Spectroscopy of the Lowest-Lying Electronic State in Sub-Critical and Supercritical Water

Marin¹,

Bartels²,

Janik³

2016

Proceedings of the 71st International Symposium on Molecular Spectroscopy

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“…We have also demonstrated that FUV spectroscopy can be effectively utilized for the quantitative and qualitative analyses of solutes in aqueous solutions because the absorption band near 150 nm due to the first electronic transition (Ã ← X) of liquid water (the ñ → σ* transition of liquid water) is very sensitive to changes in hydrogen bonding. 6,12,13 The foot of this band can be observed in the 190 -210 nm region by using an ordinary UV-Vis spectrometer. We demonstrated the potential of FUV spectroscopy in measuring minute quantities of solutes in aqueous solutions, including aqueous mixtures of NH3 and H2O2.…”

Section: Introductionmentioning

confidence: 99%

“…Using it, we investigated how the (Ã ← X) band of water is affected by the addition of solutes to water. 12,13 We utilized this new technique to monitor the quality of semiconductor wafer cleaning solutions. 8 While the ATR-FUV spectrometer is powerful in that one can observe the whole (Ã ← X) band near 150 nm of water and can investigate effects of hydration on the band, it is often enough to employ an ordinary UV-Vis spectrometer for qualitative and quantitative analysis of various aqueous solutions because one can use the foot near 200 nm of the strong 150 nm band.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Analysis of Ions in Spring Water in Three Different Areas of Hyogo Prefecture in Japan by Far Ultraviolet Spectroscopy

Mitsuoka

Shinzawa²,

Morisawa

et al. 2011

ANAL. SCI.

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“…Time-resolved photoelectron spectrum of a 30 mM NaCl solution in a) H 2 O and b) D 2 O (7.75 eV pump, 3.10 eV probe). Spectra for given delays are shown in c) for H 2 O and d) for D 2 O. Panel e) shows the time evolution of the average binding energy for the two sample solutions.…”

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confidence: 99%

Excited state dynamics of liquid water near the surface

Buchner

Ritze

Beutler

et al. 2013

EPJ Web of Conferences

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Abstract. Time resolved photoelectron spectroscopy explores the excited state dynamics of liquid water in presence of cations close to the surface. A transient hydrated electroncation complex is observed.The properties of liquid water are of fundamental importance to all natural sciences. Nevertheless, many properties of water remain poorly understood. This is particularly true for the properties and dynamics of electronic excited states, which have very short lifetimes (sub-100 fs) [1] and high excitation energies in the vacuum ultraviolet (VUV) region. Although the band maximum in bulk liquid water is near 8.4 eV [2], a lowering of the absorption edge can be expected at the surface [3]. By ab initio calculations, we show that, already at photon energies < 8 eV, the proximity of cations enables the direct excitation of a surface specific charge transfer state, leading to the formation of transient hydrated (cation. . .electron) complexes. A surface-solvated electron may thus be temporarily stabilized by subjacent cations.Time-resolved photoelectron spectroscopy of liquids is a new and promising tool to investigate excited state dynamics in solution. It has been applied to study the charge-transfer-to-solvent (CTTS) dynamics of iodide and the solvation and recombination dynamics of solvated electrons [4][5][6]. We now use this technique to study the excited state dynamics of liquid water in the presence of alkali cations at the liquid-to-vacuum interface.A detailed description of the experiment can be found elsewhere [7]. A high-pressure liquid chromatography pump pushes the sample solution (here: solutions of different salts of concentrations in the range of 30-100 mM in H 2 O or D 2 O) through a fused silica nozzle with an inner diameter of 15 µm into a vacuum chamber. A continuous liquid jet in vacuum is formed.To excite liquid water, we irradiate the liquid jet with sub-20 fs pulses at 160 nm (7.75 eV photon energy, several 10 nJ pulse energy), which are generated by non-collinear four wave mixing in an argon gas cell [8]. A delayed pulse at 400 nm (3.1 eV) or 800 nm (1.55 eV) probes the excited state by photoionization. Photoelectrons are collected by a magnetic bottle type time-of-flight spectrometer.A time-resolved photoelectron spectrum is shown in Fig. 1 a-b). After excitation of the sample (at delay ∆τ = 0), the photoelectron signal rises steeply and then decays with transient lifetimes on the fs to ps timescale (depending on solute and solvent). The average binding energy at the temporal overlap is ∼ 2.18 eV in H 2 O and ∼ 2.24 eV in D 2 O (cf. Fig. 1e). The average binding energy changes as function of delay time: it decreases within the first 100 fs and then increases. At long times, the vertical binding energy of this species in water is ∼ 2.5 eV and thus significantly smaller than the binding energy of the solvated electron in bulk water (3.3-3.7 eV, [4, 9-11]). We observe a slight cation dependence of the binding energy, while the anion does not influence the energetics. As shown in Fig. 2, the p...

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Direct observation of the absorption bands of the first electronic transition in liquid H2O and D2O by attenuated total reflectance far-UV spectroscopy

Cited by 78 publications

References 40 publications

Vacuum Ultraviolet Spectroscopy of the Lowest-Lying Electronic State in Sub-Critical and Supercritical Water

Vacuum Ultraviolet Spectroscopy of the Lowest-Lying Electronic State in Sub-Critical and Supercritical Water

Quantitative Analysis of Ions in Spring Water in Three Different Areas of Hyogo Prefecture in Japan by Far Ultraviolet Spectroscopy

Excited state dynamics of liquid water near the surface

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