Why local and non-local terms are essential for second harmonic generation simulation?

Foucaud, Yann; Dufrêche, Jean‐François; Siboulet, Bertrand; Duvail, Magali; Jonchère, Alban; Diat, Olivier; Vuilleumier, Rodolphe

doi:10.1039/d1cp05437f

Cited by 6 publications

(2 citation statements)

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“…Notably, the third layer is very similar to the next layers since the density for the third layer is not higher than the density for the other layers. The other multiple layers, identified by the density peak they form, correspond to bulk water, in which density oscillations are common due to the layered structuration of water. − Hence, the influence of the (001) WO 3 surface on the water structure was limited to two layers, which is consistent with the isosteric enthalpy of hydration.…”

Section: Resultsmentioning

confidence: 60%

Hydration Mechanisms of Tungsten Trioxide Revealed by Water Adsorption Isotherms and First-Principles Molecular Dynamics Simulations

Foucaud

Jannet

Caramori³

et al. 2023

J. Phys. Chem. C

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WO3 is one of the most interesting materials for photocatalysis due to its optical absorption in UV–vis, good charge carrier transport, and stability against photocorrosion. A detailed knowledge of the hydration state of WO3 is indispensable to gain more precise mechanistic insights into its photocatalytic activity. To the best of our knowledge, the hydration process of WO3 has been scarcely studied so far and only from a theoretical point of view, mostly by means of static density functional theory calculations. Here, we use manometric gas sorption experiments combined with extensive ab initio molecular dynamics simulations to investigate the hydration mechanisms of WO3 at room temperature. We demonstrate that water adsorbs molecularly in a two-step mechanism: the first water sublayer interacts with the under-coordinated surface tungsten atoms through electrostatic interactions, and, in a second step, a full layer is formed through hydrogen bonds established with the pre-adsorbed water molecules and with the under-coordinated surface oxygen atoms. The computed value of −90 kJ·mol–1 for the isosteric enthalpy of adsorption of the first water molecules is in excellent agreement with the experimental value estimated using the Clausius–Clapeyron approach from the experimental adsorption isotherms. The isosteric enthalpy of adsorption steadily decreases in absolute value when the surface coverage is increased to tend toward the enthalpy of condensation of water after three adsorption layers.

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Section: Resultsmentioning

confidence: 60%

Hydration Mechanisms of Tungsten Trioxide Revealed by Water Adsorption Isotherms and First-Principles Molecular Dynamics Simulations

Foucaud

Jannet

Caramori³

et al. 2023

J. Phys. Chem. C

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“…Instead of approaching the electronic degrees of freedom and the response properties of the whole liquid 34 , one performs QM polarizability and hyperpolarizability calculations for single molecules 35 . This can be performed using the response theory implemented in Dalton 16 .…”

Section: A Quantum Mechanical Observables For Second Harmonic Generat...mentioning

confidence: 99%

FROG : exploiting all-atom Molecular Dynamics trajectories to calculate linear and non-linear optical responses of molecular liquids within Dalton’s QM/MM polarizable embedding scheme

Guillaume,

Oriane,

Emmanuel

et al. 2024

Preprint

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Quantum mechanical/molecular mechanics (QM/MM) methods are interesting to model the impact of a complex environment on the spectroscopic properties of a molecule. In this context, FROG code is a tool to exploit molecular dynamics trajectories to perform QM/MM calculations of molecular optical properties. FROG stands for 'FROm molecular dynamics to second harmonic Generation' since it was developed for the calculations of hyperpolarizabilities. These are relevant to model non-linear optical intensities, and compare them with those obtained from second harmonic scattering or second harmonic generation experiments. FROG's specificity is that it is designed to study simple molecular liquids, including solvents or mixtures, from the bulk to the surface. For the QM/MM calculations, FROG relies on the Dalton package: its electronic-structure models, response theory and polarizable embedding (PE) schemes. FROG helps with the global workflow needed to deal with numerous QM/MM calculations: it permits the user to separate the system into QM and MM fragments, to write \Dalton’s inputs, to manage the submission of QM/MM calculations, to check whether \Dalton’s calculation finished successfully, and finally to perform averages on relevant QM observables. All molecules within the simulation box and several time steps are tackled within the same workflow. The platform is written in Python and installed as a package. Intermediate data such as local electric fields or individual molecular properties are accessible to the users in the form of Python object arrays. The resulting data are easily extracted, analyzed, and visualized using Python scripts that are provided in tutorials.

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Polarization-resolved second-harmonic generation: a Jones matrix approach

Kessi

2023

J Opt

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Why local and non-local terms are essential for second harmonic generation simulation?

Abstract: Both local and non-local effects are crucial to simulate the second harmonic generation signal using an ad-hoc method based on the hyperpolarisability: the chemical environment of the molecules and the quadrupolar contribution must be considered.

Cited by 6 publications

References 96 publications

Hydration Mechanisms of Tungsten Trioxide Revealed by Water Adsorption Isotherms and First-Principles Molecular Dynamics Simulations

Hydration Mechanisms of Tungsten Trioxide Revealed by Water Adsorption Isotherms and First-Principles Molecular Dynamics Simulations

FROG : exploiting all-atom Molecular Dynamics trajectories to calculate linear and non-linear optical responses of molecular liquids within Dalton’s QM/MM polarizable embedding scheme

Polarization-resolved second-harmonic generation: a Jones matrix approach

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