Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen E.; Schwegler, Eric; Galli, Giulia

doi:10.1126/sciadv.1603210

Cited by 61 publications

(73 citation statements)

References 72 publications

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“…In order to validate our computational protocol, we first compared the energies computed for the occupied electronic states of water with well-established liquid jet experimental data 13 , 36 . Consistent with our previous studies 37 , 38 , we found that the most accurate protocol for computing the binding energies of electrons in water is the G 0 W 0 approximation based on dielectric-dependent hybrid (DDH) functionals 39 , 40 . In particular, G 0 W 0 calculations with the range-separated hybrid (RSH) yielded a mean absolute error (MAE) with respect to measured spectra of only 0.18 eV for trajectories including nuclear quantum effects (NQE) and 0.38 eV for classical trajectories.…”

Section: Resultssupporting

confidence: 87%

Electron affinity of liquid water

et al. 2018

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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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Section: Resultssupporting

confidence: 87%

Electron affinity of liquid water

et al. 2018

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“…One of the problems of Li-S battery, the shuttle effect, is caused by the dissolution of lithium polysulfide (Li2Sy, 4 ≤ y ≤ 8) in the solvent. However, it is a long-standing challenge to theoretically predict the solvent behaviors of polysulfide and to calculate the solvated Gibbs formation energies of these polysulfide [19,30] . In our calculation, the charge polarizable solvent model with a fixed ion charge to determine the dielectric function profile, is used to represent the solvent effect.…”

Section: Computation Detailsmentioning

confidence: 99%

“…Thus, one has to search for the global minimum structures. The effects of solvent further complicate the issue [19] . .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of 2D Conductive Microporous Coordination Polymers as Li–S Battery Cathode with Ultrahigh Energy Density

Gao

Zheng

Pan

et al. 2018

Advanced Energy Materials

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Even though tremendous achievement has been made experimentally in the performance of Li-S battery, theoretical studies in this area are lagging behind due to the complexity of the Li-S systems and effects of solvent. For this purpose, we have developed a new methodology for investigating the 2D hexaaminobenzene-based coordination polymers (2D-HAB-CP) as cathode candidate materials for Li-S battery via density functional theory calculation in combination with in-house developed charge polarized solvent model and genetic algorithm structure global search code. With high ratios of transition metal atoms and 2-coordinated nitrogen atoms, excellent electric conductivity, and structural porosity, the 2D-HAB-CP is able to address all of the three main challenges facing Li-S battery: confining the lithium polysulfides from dissolution, facilitating the electron conductivity and buffering the volumetric expansion during the lithiation process. In addition, the theoretical energy density of this system is as high as 1395 Wh/Kg. These results demonstrated that the 2D-HAB-CP is a promising cathode material for Li-S battery. Our proposed computational framework not only opens a new avenue in understanding the key role played by solution and liquid electrolytes in Li-S battery, but also can be generally applied to other processes with liquids involved.

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“…Nevertheless periodic DFT calculations with hybrid functionals and PW basis sets remain substantially heavier, from a computational standpoint, than local or semi-local DFT calculations. The functionals PBE0 [42] and HSE [43][44][45] are among the most popular hybrid functionals used for condensed systems, and lately dielectric dependent hybrid functionals [46][47][48][49] have been increasingly used to predict structural and electronic properties of solids [46,47,[49][50][51][52][53][54][55][56][57] and liquid [58][59][60] and of several molecules [47,48,61]. Another category of orbital dependent functionals recently proposed is that of Koopmans-compliant functionals, used for both molecules and solids [62][63][64].…”

Section: Introductionmentioning

confidence: 99%

Dielectric-dependent hybrid functionals for heterogeneous materials

Zheng

Govoni

Galli

2019

Phys. Rev. Materials

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We derive a dielectric-dependent hybrid functional which accurately describes the electronic properties of heterogeneous interfaces and surfaces, as well as those of three-and two-dimensional bulk solids. The functional, which does not contain any adjustable parameter, is a generalization of self-consistent hybrid functionals introduced for homogeneous solids, where the screened Coulomb interaction is defined using a spatially varying, local dielectric function. The latter is determined self-consistently using density functional calculations in finite electric fields. We present results for the band gaps and dielectric constants of 3D and 2D bulk materials, and band offsets for interfaces, showing an accuracy comparable to that of GW calculations.

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Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Abstract: A predictive and efficient computational framework for describing the electronic properties of aqueous solutions is presented.

Cited by 61 publications

References 72 publications

Electron affinity of liquid water

Electron affinity of liquid water

Theoretical Investigation of 2D Conductive Microporous Coordination Polymers as Li–S Battery Cathode with Ultrahigh Energy Density

Dielectric-dependent hybrid functionals for heterogeneous materials

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