Ultrafast transient-absorption spectroscopy of the aqueous solvated electron

Alfano, Joseph C.; Walhout, Peter K.; Kimura, Yoshifumi; Barbara, Paul F.

doi:10.1063/1.464839

Cited by 158 publications

(125 citation statements)

References 20 publications

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“…Interestingly, the electron spin-echo patterns were later reinterpreted 2 and attributed to just two protons in the first solvation shell. In spite of this correction, the original octahedral model persists, and molecular dynamics simulations 3 with this configuration indeed captured most aspects of transient absorption spectra of solvated electrons 4 . Recent resonance Raman studies on aqueous solvated electrons 5,6 showed strongly enhanced, moderately red-shifted intramolecular bending and blue-shifted libration modes compared to bulk water and were also interpreted within the context of the original octahedral model.…”

Section: Manuscriptmentioning

confidence: 99%

Vibrational spectroscopy of hydrated electron clusters(H2O)15–50− via infrared multiple photon dissociation

Asmis

Santambrogio

Zhou³

et al. 2007

The Journal of Chemical Physics

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Infrared multiple photon dissociation spectra for size-selected water cluster anions (H2O)n−, n=15–50, are presented covering the frequency range of 560–1820cm−1. The cluster ions are trapped and cooled by collisions with ambient He gas at 20K, with the goal of defining the cluster temperature better than in previous investigations of these species. Signal is seen in two frequency regions centered around 700 and 1500–1650cm−1, corresponding to water librational and bending motions, respectively. The bending feature associated with a double-acceptor water molecule binding to the excess electron is clearly seen up to n=35, but above n=25; this feature begins to blueshift and broadens, suggesting a more delocalized electron binding motif for the larger clusters in which the excess electron interacts with multiple water molecules.

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Section: Manuscriptmentioning

confidence: 99%

Vibrational spectroscopy of hydrated electron clusters(H2O)15–50− via infrared multiple photon dissociation

Asmis

Santambrogio

Zhou³

et al. 2007

The Journal of Chemical Physics

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“…3 Another, more controversial issue is the interpretation of pump-probe excitation experiments in terms of the contributions of ground and excited state solvent reorganization dynamics and excited state population decay. 4,5,6,7,8,9,10 We focus on this issue of excited state lifetime in the present work.…”

Section: Introductionmentioning

confidence: 99%

Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron

Borgis¹,

Rossky²,

Túri³

2007

The Journal of Chemical Physics

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We present a kinetic analysis of the non-adiabatic decay mechanism of an excited state hydrated electron to the ground state. The theoretical treatment is based on a quantized, gap dependent golden rule rate constant formula which describes the non-adiabatic transition rate between two quantum states. The rate formula is expressed in terms of quantum time correlation functions of the energy gap, and of the non-adiabatic coupling. These gap dependent quantities are evaluated from three different sets of mixed quantum-classical molecular dynamics simulations of a hydrated electron equilibrated a) in its ground state, b) in its first excited state, and c) on a hypothetical mixed potential energy surface which is the average of the ground and the first excited electronic states. The quantized, gap-dependent rate results are applied in a phenomenological kinetic equation which provides the survival probability function of the excited state electron. Although the lifetime of the equilibrated excited state electron is computed to be very short (well under 100 fs), the survival probability function for the non-equilibrium process in pump-probe experiments yields an effective d

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“…20,58 An alternative route to study the interaction of electrons with water is to perform pump-probe experiments on electrons that have already been equilibrated. 39 It has been argued that the dynamics observed in this type of experiment as, for instance, the relaxation from the excited state, can be fundamentally different, because the electron has substantially changed the local solvent structure in the initial equilibration process. 64,77 The clear advantage of using pre-equilibrated electrons is that the measured transients need not be corrected for geminate recombination.…”

Section: Introductionmentioning

confidence: 99%

Wave Packet Dynamics in Ultrafast Spectroscopy of the Hydrated Electron

et al. 1998

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Hydrated-electron dynamics is examined by frequency-resolved pump-probe experiments using pulses of 13 fs centered at 780 nm. A recurrence at ∼40 fs signifies a strong coupling of the electronic transition to underdamped solvent motions. Wave packet dynamics launched by the pump pulse produces an ultrafast red-shift of the electronic transition by approximately 6500 cm -1 . Gross features of the pump-probe experiments are analyzed using a two-level system.

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Ultrafast transient-absorption spectroscopy of the aqueous solvated electron

Cited by 158 publications

References 20 publications

Vibrational spectroscopy of hydrated electron clusters(H2O)15–50− via infrared multiple photon dissociation

Vibrational spectroscopy of hydrated electron clusters(H2O)15–50− via infrared multiple photon dissociation

Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron

Wave Packet Dynamics in Ultrafast Spectroscopy of the Hydrated Electron

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