Resolving the Optical Spectrum of Water: Coordination and Electrostatic Effects

Hermann, Andreas; Schmidt, Wolf Gero; Schwerdtfeger, Peter

doi:10.1103/physrevlett.100.207403

Cited by 90 publications

(112 citation statements)

References 38 publications

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“…This behavior is mainly due to LFE, counteracting the red-shift induced by the band-gap narrowing, as an effect of intermolecular electronic interactions. [60][61][62] Moreover, contrary to the case of the d-SAM where the out-of-plane component of Im M dominates the spectrum in the considered frequency range, here Im M and Im ⊥ M show different spectral weights in specific energy regions. This is obviously related to the character of the excitations involved.…”

Section: B Optical Propertiesmentioning

confidence: 90%

Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

Cocchi

Moldt

Gahl

et al. 2016

The Journal of Chemical Physics

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In a joint theoretical and experimental work the optical properties of azobenzene-functionalized self-assembled monolayers (SAMs) are studied at different molecular packing densities. Our results, based on densityfunctional and many-body perturbation theory, as well as on differential reflectance (DR) spectroscopy, shed light on the microscopic mechanisms ruling photo-absorption in these systems. While the optical excitations are intrinsically excitonic in nature, regardless of the molecular concentration, in densely-packed SAMs intermolecular coupling and local-field effects are responsible for a sizable weakening of the exciton binding strength. Through a detailed analysis of the character of the electron-hole pairs, we show that distinct excitations involved in the photo-isomerization at low molecular concentrations are dramatically broadened by intermolecular interactions. Spectral shifts in the calculated DR spectra are in good agreement with the experimental results. Our findings represent an important step forward to rationalize the excited-state properties of these complex materials.

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Section: B Optical Propertiesmentioning

confidence: 90%

Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

Cocchi

Moldt

Gahl

et al. 2016

The Journal of Chemical Physics

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“…It has been suggested that a large fraction of molecules form only two strong HBs: one acceptor and one donor bond 2,152-156 . However, the"rings and chains" structure of liquid water 2 , as well as the inhomogeneous two-state model 152,157 implied by such an interpretation, have been challenged on many fronts 143,147,[158][159][160][161][162][163][164][165][166][167] and are a matter of an ongoing debate 80,143,147,[155][156][157][158][159][160][161][162][163][164][166][167][168][169][170][171][172] .…”

Section: Liquid Water a Structural And Dynamical Properties Of Lmentioning

confidence: 99%

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin

Kühne

2013

Phys. Chem. Chem. Phys.

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The application of newly developed first-principle modeling techniques to liquid water deepens our understanding of the microscopic origins of its unusual macroscopic properties and behaviour. Here, we review two novel ab initio computational methods: second-generation Car-Parrinello molecular dynamics and decomposition analysis based on absolutely localized molecular orbitals. We show that these two methods in combination not only enable ab initio molecular dynamics simulations on previously inaccessible time and length scales, but also provide unprecedented insights into the nature of hydrogen bonding between water molecules. We discuss recent applications of these methods to water clusters and bulk water. CONTENTS

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“…30,31 The fully periodic treatment circumvents the difficult and nonunique modeling of finite clusters and embedding, necessary, e.g., in the context of the incremental scheme. [32][33][34][35] MP2 is considered to be an accurate method for nonconducting systems, as has been recently demonstrated 36,37 on a wide variety of crystals. The random-phase approximation based on the DFT reference 38 has been reported to provide similar accuracy.…”

Section: Introductionmentioning

confidence: 99%

Electron correlation decides the stability of cubic versus hexagonal boron nitride

et al. 2011

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Original Citation:Electron correlation decides the stability of cubic versus hexagonal boron nitride. Published version:DOI:10.1103/PhysRevB.83.035117 Terms of use:Open Access (Article begins on next page) Anyone can freely access the full text of works made available as "Open Access". Works made available under a Creative Commons license can be used according to the terms and conditions of said license. Use of all other works requires consent of the right holder (author or publisher) if not exempted from copyright protection by the applicable law. Periodic local Møller-Plesset second-order perturbation theory (MP2) is applied to investigate the structural and energetic properties of the cubic and hexagonal polymorphs of boron nitride. While the Hartree-Fock (HF) solution significantly underbinds both systems and energetically favors h-BN, the post-HF correlation treatment recovers the lacking amount of the interaction energy and reverts the sign of the relative stability between the two compounds. It provides the physically correct picture and predicts cohesive energies, lattice constants, bulk moduli, and the relative stability in good agreement with experiment. Density-functional theory (DFT) results, on the other hand, are inconclusive and exhibit a strong dependence on the chosen functional. The results of MP2 as well as DFT with an empirical dispersion correction indicate that the dispersion contribution to binding is essential not only for the layered polymorph, but also (and even more so) for the cubic one. Availability: This is the author's manuscript

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Resolving the Optical Spectrum of Water: Coordination and Electrostatic Effects

Cited by 90 publications

References 38 publications

Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Electron correlation decides the stability of cubic versus hexagonal boron nitride

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