A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

Raupach, Marc; Tonner, Ralf

doi:10.1063/1.4919943

Cited by 86 publications

(115 citation statements)

References 128 publications

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“…69,70 Moreover, they treat both inter-and intramolecular 18,19,43,71 (including through-bond) interactions on equal footing (including through bond) and, thus, capably describe phenomena that are of a mixed or non-covalent nature, e.g., dative bonds, 27,72,73 as well as chemisorption and physisorption processes 221,222 (through a "periodic EDA" by Tonner et al 223 ). Owing to the numerous levels of accuracy possible, including multireference variants, 41,74 it is also possible to treat strongly correlated systems 75 and molecules having elongated bonds.…”

Section: Figmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

104

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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Section: Figmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

104

102

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“…Chemical interactions are also described by Energy Decomposition Analysis (EDA), 39,40 Constrained Space Orbital Variation (CSOV), 41,42 Natural Energy Decomposition Analysis-NEDA, 43,44,45 localized molecular orbitals EDA, 46,47 and more recently periodic energy decomposition analysis (pEDA). 48 52,53 where interactions are decomposed into  and  contributions.…”

Section: Quantum Theory Of Atoms In Molecules (Qtaim) Applied To Co Amentioning

confidence: 99%

Electron density topological and adsorbate orbital analyses of water and carbon monoxide co-adsorption on platinum

Dimakis

Salas

Gonzalez³

et al. 2019

The Journal of Chemical Physics

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The electron density topology of carbon monoxide (CO) on dry and hydrated platinum is evaluated under the quantum theory of atoms in molecules (QTAIM) and by adsorbate orbital approaches. The impact of water co-adsorbate on the electronic, structural, and vibrational properties of CO on Pt are modelled by periodic density functional theory (DFT). At low CO coverage, increased hydration weakens C–O bonds and strengthens C–Pt bonds, as verified by changes in bond lengths and stretching frequencies. These results are consistent with QTAIM, the 5σ donation-2π* backdonation model, and our extended π-attraction σ-repulsion model (extended π-σ model). This work links changes in the non-zero eigenvalues of the electron density Hessian at QTAIM bond critical points to changes in the π and σ C–O bonds with systematic variation of CO/H2O co-adsorbate scenarios. QTAIM invariably shows bond strengths and lengths as being negatively correlated. For atop CO on hydrated Pt, QTAIM and phenomenological models are consistent with a direct correlation between C–O bond strength and CO coverage. However, DFT modelling in the absence of hydration shows that C–O bond lengths are not negatively correlated to their stretching frequencies, in contrast to the Badger rule: When QTAIM and phenomenological models do not agree, the use of the non-zero eigenvalues of the electron density Hessian as inputs to the phenomenological models, aligns them with QTAIM. The C–O and C–Pt bond strengths of bridge and three-fold bound CO on dry and hydrated platinum are also evaluated by QTAIM and adsorbate orbital analyses.

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“…A similar model have been recently developed for extended systems. [11] Calculations performed by the authors of Ref. 5-7, showed that for some system the ionic relaxation (changes in the molecular structure) effect is significant.…”

Section: Introductionmentioning

confidence: 98%

“…9 and 10. A similar model have been recently developed for extended systems . Calculations performed by the authors of Ref.…”

Section: Introductionmentioning

confidence: 99%

On the Elusive Link between Adsorbate's Binding Energy and Bond Strength: An Illustration from CO Adsorption on Metal-Doped Graphene

2017

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Adsorbates’ binding energy is often used as an indicator of the adsorbate‐substrate bond strength. Although one can compute any binding energy, models to gauge bond‐strength are developed to rationalize and anticipate it for the rational search for efficient catalysts. Unfortunately, bond‐strength alone fails to predict trends in binding energy because, as hinted by models since the 1970s, the binding energy is the outcome of a complex response of the system to the created bond. Therefore further understanding the difference between binding energy and bond strength is essential to catalysts design. Indeed, the adsorbate‐substrate bond formation perturbs, not only the geometry of the system, but also the substrate and adsorbate's electronic charge density. Both effects overall reduce the binding energy by an energy attached to such perturbations, the so‐called perturbation energy. Here, with the example of carbon monoxide adsorption on metal‐doped graphene, we show that such perturbation energy may exceed 1 eV and render an unusual situation: Namely, although the binding energy of CO to the Au‐doped graphene indicates that binding does not happen, we find evidence of a strong bond between CO and such substrate. Thus, in this case, the large perturbation energy totally disrupts the equivalency between bond strength and binding energy. Here we propose a method to compute the perturbation energy that bypasses dealing with an excited electronic state of the system.

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A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

Cited by 86 publications

References 128 publications

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Electron density topological and adsorbate orbital analyses of water and carbon monoxide co-adsorption on platinum

On the Elusive Link between Adsorbate's Binding Energy and Bond Strength: An Illustration from CO Adsorption on Metal-Doped Graphene

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