Retrapping and solvation dynamics after femtosecond UV excitation of the solvated electron in water

Assel, M.; Laenen, R.; Laubereau, A.

doi:10.1063/1.479979

Cited by 77 publications

(70 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since their discovery over 40 years ago, 1 solvated electrons have been the subject of great interest: their large absorption cross sections make them amenable to study by ultrafast spectroscopy, [2][3][4][5] and their simple electronic structure allows for detailed theoretical analysis via quantum simulation. [6][7][8][9][10][11] Figure 1 shows the optical absorption spectra of solvated electrons in several different solvents, reproduced from the Gaussian-Lorentzian fitting parameters given in Ref.…”

Section: Introductionmentioning

confidence: 99%

The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

Bedard-Hearn¹,

Larsen²,

Schwartz³

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran ͑THF͒, the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little FranckCondon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels ͑e.g., s-like, p-like͒ are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated.

show abstract

Section: Introductionmentioning

confidence: 99%

The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

Bedard-Hearn¹,

Larsen²,

Schwartz³

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…257 These results, however, were later challenged by both theoretical 242,266,19 and experimental studies. 36,258,259,267 We mention here Shkrob's analysis that points to a possible source of the discrepancies in the application of soft (less repulsive) versus hard (more repulsive) pseudopotentials in the one-electron simulations. 266 Larsen et al reached a similar conclusion using their non-cavity preferring pseudopotential, 19 but Herbert and Jacobson have reported that the lack of polarized hole burning dynamics is not necessarily inconsistent with the cavity model itself.…”

mentioning

confidence: 99%

Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

2012

View full text Add to dashboard Cite

“…It is intuitively explicable that the cross section of such reactions is strongly connected to the excited electron lifetimes, because a longer availability of the localized charge enhances the probability of an encounter with the reactant. With regard to time-resolved studies of excess electrons in clusters 7,[18][19][20][21] and the liquid phase, 8,[22][23][24][25] it should be noted that these investigations have mainly focused on the dynamics occurring after photoexcitation from the ground (s-type) to the excited (p-type) state, i.e. the relaxation dynamics of the formerly equilibrated system that is perturbed by laser excitation.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the excitation of e T via the n ¼ 1 image potential state provides information about the maximum distance of the trapped electrons from the metal surface, because electron population transfer from the IPS to e T is only feasible for adjacent wave functions. Thus, the [20][21][22][23][24][25][26][27][28][29][30] A, which the IPS extends to vacuum, give a conservatively estimated upper limit for the excess electron distance from the metal surface.…”

mentioning

confidence: 99%

Solvation dynamics of surface-trapped electrons at NH3 and D2O crystallites adsorbed on metals: from femtosecond to minute timescales

et al. 2011

View full text Add to dashboard Cite

The creation and stabilization of localized, low-energy electrons is investigated in polar molecular environments. We create such excess electrons in excited states in ice and ammonia crystallites adsorbed on metal surfaces and observe their relaxation in real time using time-resolved photoelectron spectroscopy. The observed dynamics proceed up to minute timescales and are therefore slowed down considerably compared to ultrafast excited state relaxation in front of metal surfaces, which proceeds typically on femto-or picosecond time scales. It is the highly efficient wave function constriction of the electrons from the metal that ultimately enables the investigation of the relaxation dynamics over a large range of timescales (up to 17 orders of magnitude). Therefore, it gives novel insight into the solvated electron ground state formation at interfaces. As these long-lived electrons are observed for both, D 2 O and NH 3 crystallites, they appear to be of general character for polar molecule-metal interfaces. Their time-and temperature-dependent relaxation is analyzed for both, crystalline ice and ammonia, and compared using an empirical model that yields insight into the fundamental solvation processes of the respective solvent.

show abstract

Retrapping and solvation dynamics after femtosecond UV excitation of the solvated electron in water

Abstract: Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopy

Cited by 77 publications

References 36 publications

The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

Solvation dynamics of surface-trapped electrons at NH3 and D2O crystallites adsorbed on metals: from femtosecond to minute timescales

Contact Info

Product

Resources

About