Electron Affinity of Liquid Water

Overview

Journal Nat Commun

Specialty Biology

Date 2018 Jan 18

PMID 29339731

Citations 28

Authors

Alex P Gaiduk

Tuan Anh Pham

Marco Govoni

Francesco Paesani

Giulia Galli

Affiliations

Soon will be listed here.

Abstract

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential of the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.

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References

Zhang L, Zhu D, Nathanson G, Hamers R . Selective photoelectrochemical reduction of aqueous CO₂ to CO by solvated electrons. Angew Chem Int Ed Engl. 2014; 53(37):9746-50. DOI: 10.1002/anie.201404328. View

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

Del Ben M, Hutter J, VandeVondele J . Probing the structural and dynamical properties of liquid water with models including non-local electron correlation. J Chem Phys. 2015; 143(5):054506. DOI: 10.1063/1.4927325. View

Elles C, Jailaubekov A, Crowell R, Bradforth S . Excitation-energy dependence of the mechanism for two-photon ionization of liquid H(2)O and D(2)O from 8.3 to 12.4 eV. J Chem Phys. 2006; 125(4):44515. DOI: 10.1063/1.2217738. View

Jacobson L, Herbert J . Polarization-bound quasi-continuum states are responsible for the "blue tail" in the optical absorption spectrum of the aqueous electron. J Am Chem Soc. 2010; 132(29):10000-2. DOI: 10.1021/ja1042484. View

Prendergast D, Grossman J, Galli G . The electronic structure of liquid water within density-functional theory. J Chem Phys. 2005; 123(1):014501. DOI: 10.1063/1.1940612. View

Stahler J, Deinert J, Wegkamp D, Hagen S, Wolf M . Real-time measurement of the vertical binding energy during the birth of a solvated electron. J Am Chem Soc. 2015; 137(10):3520-4. DOI: 10.1021/ja511571y. View

Giannozzi P, Baroni S, Bonini N, Calandra M, Car R, Cavazzoni C . QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J Phys Condens Matter. 2011; 21(39):395502. DOI: 10.1088/0953-8984/21/39/395502. View

Adriaanse C, Cheng J, Chau V, Sulpizi M, VandeVondele J, Sprik M . Aqueous Redox Chemistry and the Electronic Band Structure of Liquid Water. J Phys Chem Lett. 2015; 3(23):3411-5. DOI: 10.1021/jz3015293. View

10.

Marsalek O, Uhlig F, VandeVondele J, Jungwirth P . Structure, dynamics, and reactivity of hydrated electrons by ab initio molecular dynamics. Acc Chem Res. 2011; 45(1):23-32. DOI: 10.1021/ar200062m. View

11.

Siefermann K, Liu Y, Lugovoy E, Link O, Faubel M, Buck U . Binding energies, lifetimes and implications of bulk and interface solvated electrons in water. Nat Chem. 2010; 2(4):274-9. DOI: 10.1038/nchem.580. View

12.

Elles C, Rivera C, Zhang Y, Pieniazek P, Bradforth S . Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy. J Chem Phys. 2009; 130(8):084501. DOI: 10.1063/1.3078336. View

13.

Wan Q, Spanu L, Galli G, Gygi F . Raman Spectra of Liquid Water from Ab Initio Molecular Dynamics: Vibrational Signatures of Charge Fluctuations in the Hydrogen Bond Network. J Chem Theory Comput. 2015; 9(9):4124-30. DOI: 10.1021/ct4005307. View

14.

Donald W, Demireva M, Leib R, Aiken M, Williams E . Electron hydration and ion-electron pairs in water clusters containing trivalent metal ions. J Am Chem Soc. 2010; 132(13):4633-40. DOI: 10.1021/ja9079385. View

15.

Zhu D, Zhang L, Ruther R, Hamers R . Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat Mater. 2013; 12(9):836-41. DOI: 10.1038/nmat3696. View

16.

Medders G, Babin V, Paesani F . Development of a "First-Principles" Water Potential with Flexible Monomers. III. Liquid Phase Properties. J Chem Theory Comput. 2015; 10(8):2906-10. DOI: 10.1021/ct5004115. View

17.

Boero M, Parrinello M, Terakura K, Ikeshoji T, Liew C . First-principles molecular-dynamics simulations of a hydrated electron in normal and supercritical water. Phys Rev Lett. 2003; 90(22):226403. DOI: 10.1103/PhysRevLett.90.226403. View

18.

Vanderbilt . Optimally smooth norm-conserving pseudopotentials. Phys Rev B Condens Matter. 1985; 32(12):8412-8415. DOI: 10.1103/physrevb.32.8412. View

19.

Gaiduk A, Govoni M, Seidel R, Skone J, Winter B, Galli G . Photoelectron Spectra of Aqueous Solutions from First Principles. J Am Chem Soc. 2016; 138(22):6912-5. DOI: 10.1021/jacs.6b00225. View

20.

Van De Walle CG , Martin . Theoretical study of band offsets at semiconductor interfaces. Phys Rev B Condens Matter. 1987; 35(15):8154-8165. DOI: 10.1103/physrevb.35.8154. View