Band gaps of liquid water and hexagonal ice through advanced electronic-structure calculations

Bischoff, Thomas; Reshetnyak, Igor; Pasquarello, Alfredo

doi:10.1103/physrevresearch.3.023182

Cited by 30 publications

(38 citation statements)

References 156 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…26,28 In particular, this set-up yields a Kohn-Sham band gap of 8.8 eV for liquid water, 49 in agreement with recent bounds set for the experimental value. 50 All the periodic AIMD calculations are performed with the CP2K code 51 employing TZV2P basis sets 52 and Goedecker-Teter-Hutter pseudopotentials. 53,54 The exchange integrals are calculated with the auxiliary density matrix method.…”

Section: Methodsmentioning

confidence: 99%

Evolution of Aqueous Electron with Varying Temperature

Lan

Рыбкин²,

Pasquarello

2022

Preprint

Self Cite

View full text Add to dashboard Cite

The temperature-dependent properties of the aqueous electron have been extensively studied using mixed quantum-classical simulations in a wide range of thermodynamic conditions based on one-electron pseudopotentials. While the cavity model appears to explain most of the physical properties of the aqueous electron, only a non-cavity model has so far been successful in accounting for the temperature dependence of the absorption spectrum. Here, we present an accurate and efficient description of the aqueous electron under various thermodynamic conditions by combining hybrid functional-based molecular dynamics, machine learning techniques, and multiple time-step methods. Our advanced simulations accurately describe the temperature dependence of the absorption maximum in the presence of cavity formation. Specifically, our work reveals that the red shift of the absorption maximum results from an increasing gyration radius with temperature, rather than from global density variations as previously suggested.

show abstract

Section: Methodsmentioning

confidence: 99%

Evolution of Aqueous Electron with Varying Temperature

Lan

Рыбкин²,

Pasquarello

2022

Preprint

Self Cite

View full text Add to dashboard Cite

show abstract

“…[95,96] In practice, we find the high energy band displays a very small dependence of the selected configuration, in line with other studies. [97] The thermalized configurations are used as input for the DFT calculations, which are used to relax the intramolecular degrees of freedom of the H 2 O molecules.…”

Section: Improved Oscillator Modelmentioning

confidence: 99%

“…[101] To solve the Kohn-Sham equations, we employ the Vienna Ab innitio Simulation Package (VASP), [52][53][54] using a plane wave basis set with cutoff at 700 eV for the valence electrons, and core electrons treated with pseudopotentials in the projected augmented wave approximation (PAW). [105,106] In order to obtain the optical properties in the high energy region, results from the PBE calculations are post processed under the GW/RPA approximation, [56,57,97]. For further details, the reader is referred to references [58,59].…”

Section: Improved Oscillator Modelmentioning

confidence: 99%

Intermolecular forces at ice and water interfaces: premelting, surface freezing and regelation

Luengo-Marquez,

Izquierdo-Ruiz,

MacDowell

2022

Preprint

View full text Add to dashboard Cite

Using Lifshitz theory we assess the role of van der Waals forces at interfaces of ice and water. The results are combined with measured structural forces from computer simulations to develop a quantitative model of the surface free energy of premelting films. This input is employed within the framework of wetting theory and allows us to predict qualitatively the behavior of quasi-liquid layer thickness as a function of ambient conditions. Our results emphasizes the significance of vapor pressure. The ice vapor interface is shown to exhibit only incomplete premelting, but the situation can shift to a state of complete surface melting above water saturation. The results obtained serve also to assess the role of subsurface freezing at the water-vapor interface, and we show that intermolecular forces favor subsurface ice nucleation only in conditions of water undersaturation. We show ice regelation at ambient pressure may be explained as a process of capillary freezing, without the need to invoke the action of bulk pressure melting. Our results for van der Waals forces are exploited in order to gauge dispersion interactions in empirical point charge models of water.

show abstract

“…Many-body perturbation theory in the GW approximation 11 is currently recognized as the most accurate scheme for band-gap calculations, especially in its selfconsistent quasiparticle formulation including vertex corrections in the screening. [12][13][14][15] However, such calculations are computationally highly demanding and cannot be envisaged as an efficient tool for screening large databases.…”

Section: Introductionmentioning

confidence: 99%

“…[20][21][22] It has been shown that the higher accuracy can be achieved through material-specific dielectric-dependent hybrid (DDH) functionals. 14,[23][24][25][26][27][28] Alkauskas et al 23 and Marques et al 24 linked the incorporated amount of Fock exchange to the inverse high-frequency dielectric constant 1/ ∞ . Next, Skone et al developed range-separated DDH functionals in which 1/ ∞ determines the fraction of Fock exchange in the long range (LR), while retaining the same mixing parameter of the global PBE0 (0.25) in the short range (SR).…”

Section: Introductionmentioning

confidence: 99%

Accurate and efficient band-gap predictions for metal halide perovskites at finite temperature

Wang¹,

Tal²,

Bischoff³

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

We develop a computationally efficient scheme to accurately determine finite-temperature band gaps. We here focus on materials belonging to the class ABX 3 (A = Rb, Cs; B = Ge, Sn, Pb; and X = F, Cl, Br, I), which includes halide perovskites.First, an initial estimate of the band gap is provided for the ideal crystalline structure through the use of a range-separated hybrid functional, in which the parameters are determined nonempirically from the electron density and the high-frequency dielectric constant. Next, we consider two kinds of band-gap corrections to account for spin-orbit coupling and thermal vibrations including zero-point motions. In particular, the latter effect is accounted for through the special displacement method, which consists in using a single distorted configuration obtained from the vibrational frequencies and eigenmodes, thereby avoiding lengthy molecular dynamics. The sequential consideration of both corrections systematically improves the band gaps, reaching a mean absolute error of 0.17 eV with respect to experimental values. The computational efficiency of our scheme stems from the fact that only a single calculation at the hybrid-functional

show abstract

Band gaps of liquid water and hexagonal ice through advanced electronic-structure calculations

Cited by 30 publications

References 156 publications

Evolution of Aqueous Electron with Varying Temperature

Evolution of Aqueous Electron with Varying Temperature

Intermolecular forces at ice and water interfaces: premelting, surface freezing and regelation

Accurate and efficient band-gap predictions for metal halide perovskites at finite temperature

Contact Info

Product

Resources

About