Hydrogen Atom Transfer from Water or Alcohols Activated by Presolvated Electrons

Iglev, Hristo; Kolev, S.; Rossmadl, Hubert; Petkov, P.; Vayssilov, Georgi N.

doi:10.1021/acs.jpclett.5b00288

Cited by 7 publications

(16 citation statements)

References 40 publications

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“…The solvated electron constitutes an intriguing phenomenon that has continued to draw attention since its discovery. − Understanding the trends and peculiarities of electron solvation in different solvents is helpful to a variety of fields, including radiation chemistry, energy storage, and organic synthesis. Solvated electrons are particularly interesting in the context of electron-transfer phenomena.…”

Section: Introductionmentioning

confidence: 99%

Electron Solvation in Liquid Ammonia: Lithium, Sodium, Magnesium, and Calcium as Electron Sources

Chaban

Prezhdo

2016

J. Phys. Chem. B

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A free electron in solution, known as a solvated electron, is the smallest possible anion. Alkali and alkaline earth atoms serve as electron donors in solvents that mediate outer-sphere electron transfer. We report herein ab initio molecular dynamics simulations of lithium, sodium, magnesium, and calcium in liquid ammonia at 250 K. By analyzing the electronic properties and the ionic and solvation structures and dynamics, we systematically characterize these metals as electron donors and ammonia molecules as electron acceptors. We show that the solvated metal strongly modifies the properties of its solvation shells and that the observed effect is metal-specific. Specifically, the radius and charge exhibit major impacts. The single solvated electron present in the alkali metal systems is distributed more uniformly among the solvent molecules of each metal's two solvation shells. In contrast, alkaline earth metals favor a less uniform distribution of the electron density. Alkali and alkaline earth atoms are coordinated by four and six NH3 molecules, respectively. The smaller atoms, Li and Mg, are stronger electron donors than Na and Ca. This result is surprising, as smaller atoms in a column of the periodic table have higher ionization potentials. However, it can be explained by stronger electron donor-acceptor interactions between the smaller atoms and the solvent molecules. The structure of the first solvation shell is sharpest for Mg, which has a large charge and a small radius. Solvation is weakest for Na, which has a small charge and a large radius. Weak solvation leads to rapid dynamics, as reflected in the diffusion coefficients of NH3 molecules of the first two solvation shells and the Na atom. The properties of the solvated electrons established in the present study are important for radiation chemistry, synthetic chemistry, condensed-matter charge transfer, and energy sources.

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Section: Introductionmentioning

confidence: 99%

Electron Solvation in Liquid Ammonia: Lithium, Sodium, Magnesium, and Calcium as Electron Sources

Chaban

Prezhdo

2016

J. Phys. Chem. B

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“…Solvated electron, which can be stabilized in a solvent by polarizing its surrounding, is one of the most fundamental chemical reagents of intense experimental and theoretical interest. − Since their discovery in intense blue coloration in solutions of alkali metals in ammonia, solvated electrons have been found to be important negative charge carriers that are also closely related to proton transfer. − Therefore, the investigation on solvated electrons has significance in physics, chemistry, and biology.…”

mentioning

confidence: 99%

“…Most experimental and theoretical investigations of solvated electrons have focused on elucidating their equilibrium structure and solvation dynamics in a variety of neat liquids. − ,,− ,,,,,,,− It is well established that an excess electron can be bound by dipolar forces to surfaces of small H 2 O clusters. − Ab initio calculations show that such partially hydrated or “wet” electrons on clusters are bound to the “dangling” H atoms, which do not form strong hydrogen bonds (HBs). ,,,, The dynamics of such solvated, dubbed “wet” electrons are intensively studied. ,,,− ,− ,− ,,,, …”

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confidence: 99%

Tuning Solvated Electrons by Polar–Nonpolar Oxide Heterostructure

Wang

Guo

Zheng

et al. 2018

J. Phys. Chem. Lett.

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Solvated electron states at the oxide/aqueous interface represent the lowest energy charge-transfer pathways, thereby playing an important role in photocatalysis and electronic device applications. However, their energies are usually higher than the conduction band minimum (CBM), which makes the solvated electrons difficult to utilize in charge-transfer processes. Thus it is essential to stabilize the energy of the solvated electron states. Taking LaAlO/SrTiO (LAO/STO) oxide heterostructure with HO-adsorbed monolayer as a prototypical system, we show using DFT and ab initio time-dependent nonadiabatic molecular dynamics simulation that the energy and dynamics of solvated electrons can be tuned by the electric field in the polar-nonpolar oxide heterostructure. In particular, for LAO/STO with p-type interface, the CBM is contributed by the solvated electron state when LAO is thicker than four unit cells. Furthermore, the solvated electron band minimum can be partially occupied when LAO is thicker than eight unit cells. We propose that the tunability of solvated electron states can be achieved on polar-nonpolar oxide heterostructure surfaces as well as on ferroelectric oxides, which is important for charge and proton transfer at oxide/aqueous interfaces.

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“…These previous studies constitute a motion picture of an excess electron, which first delocalizes in the conduction band and then is solvated within about 1 to 2 ps. [4][5][6][7][8][9][10][11][12][13] This process is considered to include many transient and highly active intermediates, resulting in a large blueshift in the absorption spectrum, from the THz or gigahertz region to the visible range. Nonetheless, previous studies mainly investigated the behavior of low-density quasifree electrons excited by small pump power density, which is far from enough for further understanding the transient evolution of photoexcited plasma in liquid water.…”

Section: Introductionmentioning

confidence: 99%

Transient evolution of quasifree electrons of plasma in liquid water revealed by optical-pump terahertz-probe spectroscopy

et al. 2021

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The fundamental properties of laser-induced plasma in liquid water, such as the ultrafast electron migration and solvation, have not yet been clarified. We use 1650-nm femtosecond laser pulses to induce the plasma in a stable free-flowing water film under the strong field ionization mechanism. Moreover, we adopt intense terahertz (THz) pulses to probe the ultrafast temporal evolution of quasifree electrons of the laserinduced plasma in water on the subpicosecond scale. For the first time, the THz wave absorption signal with a unique two-step decay characteristic in time domain is demonstrated, indicating the significance of electron solvation in water. We employ the Drude model combined with the multilevel intermediate model and particlein-a-box model to simulate and analyze the key information of quasifree electrons, such as the frequencydomain absorption characteristics and solvation ratio. In particular, we observe that the solvation capacity of liquid water decreases with the increase of pumping energy. Up to ∼50% of quasifree electrons cannot be captured by traps associated with the bound states as the pumping energy increases to 90 μJ∕pulse. The ultrafast electron evolution in liquid water revealed by the optical-pump/THz-probe experiment provides further insights into the formation and evolution mechanisms of liquid plasma.

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Hydrogen Atom Transfer from Water or Alcohols Activated by Presolvated Electrons

Cited by 7 publications

References 40 publications

Electron Solvation in Liquid Ammonia: Lithium, Sodium, Magnesium, and Calcium as Electron Sources

Electron Solvation in Liquid Ammonia: Lithium, Sodium, Magnesium, and Calcium as Electron Sources

Tuning Solvated Electrons by Polar–Nonpolar Oxide Heterostructure

Transient evolution of quasifree electrons of plasma in liquid water revealed by optical-pump terahertz-probe spectroscopy

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