Solvation dynamics of the hydrated electron: A nonadiabatic quantum simulation

Webster, Frank; Schnitker, Jürgen; Friedrichs, Mark S.; Friesner, Richard A.; Rossky, Peter J.

doi:10.1103/physrevlett.66.3172

Cited by 244 publications

(205 citation statements)

References 20 publications

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“…In this case, ultrafast pump-probe experiments by Barbara's group indicate a k (H) /k (D) = 1.4 in comparing the ground-state recovery of an excess electron in water versus heavy water 22 . The effect was largely attributed to the quantum mechanical librational modes of the surrounding solvent cavity [23][24][25][26][27] .…”

Section: Discussionmentioning

confidence: 99%

Isotopic effect and temperature dependent intramolecular excitation energy transfer in a model donor–acceptor dyad

Singh

Bittner

2010

Phys. Chem. Chem. Phys.

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We consider here the non-adiabatic energy transfer dynamics for a model bi-chromophore system consisting of a perylenediimide unit linked to a ladder-type poly-(para-phenylene) oligomer. Starting from a semi-empirical parameterization of a model electron/phonon Hamiltonian, we compute the golden-rule rate for energy transfer from the LPPP5 donor to the PDI acceptor. Our results indicate that the non-adiabatic transfer is promoted by the out-of-plane wagging modes of the C-H bonds even though theses modes give little or no contribution to the Franck Condon factors in this system. We also predict a kinetic isotope effect of k (H) /k (D) = 1.7 − 2.5 depending upon the temperature.

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Section: Discussionmentioning

confidence: 99%

Isotopic effect and temperature dependent intramolecular excitation energy transfer in a model donor–acceptor dyad

Singh

Bittner

2010

Phys. Chem. Chem. Phys.

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“…It is not surprising that kZ is the same for the two mechanisms since we interpret k, to be an excited state relaxation process from the lowest excited electron state (wet electron) to its ground state (solvated electron) [ 27,33,34,37,40,421. Unless the proximity of the wet electron to the H,O+ and OH' species perturbs this relaxation, we should expect the excited state relaxation rate constant k2 to be the same for the two-and three-photon mechanisms.…”

Section: Possible Model For Intensity-dependent Kinetics Let Us Now Cmentioning

confidence: 99%

Intensity dependent geminate recombination in water

Long

Shi

et al. 1991

Chemical Physics Letters

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We have observed an intensity dependent geminate recombination of electrons in neat water. Since the recombination dynamics occurs on a time scale comparable to the salvation dynamics, the kinetics characteristic of an isosbestic wavelength are obscured. We have hypothesized that this intensity-dependent geminate recombination is due to the existence of two mechanisms for electron production with different characteristic thermalization distances. These results clarify the discrepancy between cxperiments at higher intensities and those at lower intensities

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“…In contrast, AIMD/PBE simulations predict that, in liquid EC, the excess e − is initially delocalized within one or more EC molecules, unlike in water where excess e − occupies intermolecular spaces stabilized by hydrogen-bond donors. 24 When instantaneous favorable molecular geometries localize the e − on one EC and substantially populates orbitals on C and O atoms (Fig. 2a), bond-breaking pathways with rates different from that in the gas phase emerge.…”

mentioning

confidence: 99%

Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes

Leung

Budzien

2010

Phys. Chem. Chem. Phys.

259

361

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The decomposition of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase (SEI) films at the solvent-graphitic anode interface is critical to lithium ion battery operations. Ab initio molecular dynamics simulations of explicit liquid EC/graphite interfaces are conducted to study these electrochemical reactions. We show that carbon edge terminations are crucial at this stage, and that achievable experimental conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decomposition products seen in experiments but not previously predicted.Improving the fundamental scientific understanding of lithium ion batteries 1-3 is critical for electric vehicles and efficient use of solar and wind energy. A key limitation in current batteries is their reliance on passivating solid electrolyte interphase (SEI) films on graphitic anode surfaces. 1-5 Upon first charging of a pristine battery, the large negative potential applied to induce Li + intercalation into graphite decomposes ethylene carbonate (EC, Fig. 1) molecules in the solvent, yielding a self-limiting, 30-50 nm thick, passivating SEI layer containing Li 2 CO 3 , lithium ethylene dicarbonate ((CH 2 CO 3 Li) 2 ), 2,4-6 and salt decomposition products. C 2 H 4 and CO gases have also been detected 7,8 and shown to come from EC. 9 Similar reactions occur during power cycling when the SEI film cracks and graphite is again exposed to EC. 2 If instead the solvent is pure propylene carbonate (PC), a stable SEI film does not materialize 1,2 and the battery fails. Our work shows that novel mechanisms for the initial stages of SEI-growth at electrode-electrolyte interfaces can be simulated within time scales accessible to ab initio molecular dynamics (AIMD), 10 which have successfully modelled liquid-solid interfaces. 11 AIMD is likely also applicable to shed light on cosolvent/additives which must decompose more readily than EC to alter and improve SEI structure, Li + transport, and passivating properties. 1,2 EC-decomposition mechanisms under electron-rich conditions have been proposed (e.g., Refs. 4,5) and investigated using gas cluster Density Functional Theory calculations with and without dielectric continuum approximation of the liquid environment. 12-15 Thus "EC − ", coordinated to Li + or otherwise, has been predicted to undergo ethylene carbon (C E )-oxygen (O 1 ) bond cleavage to form a more stable radical anion (Figs. 1a-b). The potential energy barrier involved is at least 0.33 eV. 12,14 Carbonyl carbon (C C )-O 1 bond-"breaking" (or elongation) in the gas phase EC − -Li + complex yields a lower barrier, but metastable products. 14 Unlike these previous work, AIMD simulations can include explicit liquid state environments and EC/graphite interfaces. Unlike classical force field-based simulations, 16,17 AIMD accounts for covalent bondbreaking. We apply the VASP code, 18,19 the PerdewBurke-Ernzerhof (PBE) functional, 20 Γ-point Brillouin zone sampling, 400 eV planewave energy cutoff, tritium masses for all protons to allow B...

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Solvation dynamics of the hydrated electron: A nonadiabatic quantum simulation

Cited by 244 publications

References 20 publications

Isotopic effect and temperature dependent intramolecular excitation energy transfer in a model donor–acceptor dyad

Isotopic effect and temperature dependent intramolecular excitation energy transfer in a model donor–acceptor dyad

Intensity dependent geminate recombination in water

Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes

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