The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

The Sabatier principle, which states that the binding energy between the catalyst and the reactant should be neither too strong nor too weak, has been widely used as the key criterion in designing and screening electrocatalytic materials necessary to promote the sustainability of our society. The widespread success of density functional theory (DFT) has made binding energy calculations a routine practice, turning the Sabatier principle from an empirical principle into a quantitative predictive tool. Given its importance in electrocatalysis, we have attempted to introduce the reader to the fundamental concepts of the Sabatier principle with a highlight on the limitations and challenges in its current thermodynamic context. The Sabatier principle is situated at the heart of catalyst development, and moving beyond its current thermodynamic framework is expected to promote the identification of next-generation electrocatalysts.

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A DFT study of spherands containing five anisyl groups — Highly preorganized to bind the alkali metal

Canadian Journal of Chemistry ◽

10.1139/v06-130 ◽

2006 ◽

Vol 84 (8) ◽

pp. 1045-1049 ◽

Cited By ~ 4

Author(s):

Shabaan AK Elroby ◽

Kyu Hwan Lee ◽

Seung Joo Cho ◽

Alan Hinchliffe

Keyword(s):

Density Functional Theory ◽

Binding Energy ◽

Density Functional ◽

Ionic Radius ◽

Binding Energies ◽

Cavity Size ◽

X Ray Diffraction ◽

Functional Theory ◽

X Ray ◽

Good Agreement

Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygens during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. We used standard B3LYP/6-31G** (5d) density functional theory (DFT) to investigate the complexation between spherands containing five anisyl groups, with CH2–O–CH2 (2) and CH2–S–CH2 (3) units in an 18-membered macrocyclic ring, and the cationic guests (Li+, Na+, and K+). Our geometric structure results for spherands 1, 2, and 3 are in good agreement with the previously reported X-ray diffraction data. The absolute values of the binding energy of all the spherands are inversely proportional to the ionic radius of the guests. The results, taken as a whole, show that replacement of one anisyl group by CH2–O–CH2 (2) and CH2–S–CH2 (3) makes the cavity bigger and less preorganized. In addition, both the binding and specificity decrease for small ions. The spherands 2 and 3 appear beautifully preorganized to bind all guests, so it is not surprising that their binding energies are close to the parent spherand 1. Interestingly, there is a clear linear relation between the radius of the cavity and the binding energy (R2 = 0.999).Key words: spherands, preorganization, density functional theory, binding energy, cavity size.

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Exact Second-Order Corrections and Accurate Quasiparticle Energy Calculations in Density Functional Theory

The Journal of Physical Chemistry Letters ◽

10.1021/acs.jpclett.1c01962 ◽

2021 ◽

pp. 7236-7244

Author(s):

Yuncai Mei ◽

Zehua Chen ◽

Weitao Yang

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Second Order ◽

Functional Theory ◽

Energy Calculations ◽

Quasiparticle Energy

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Structural Properties, Natural Bond Orbital, Density Functional Theory (DFT) and Energy Calculations for Fluorous Compound: C13H12F7ClN2O

Current Research in Chemistry ◽

10.3923/crc.2014.16.21 ◽

2013 ◽

Vol 6 (1) ◽

pp. 16-21

Author(s):

Shahriar Ghammamy ◽

Masomeh Shahsavary ◽

Amir Lashgari

Keyword(s):

Density Functional Theory ◽

Structural Properties ◽

Density Functional ◽

Natural Bond Orbital ◽

Functional Theory ◽

Energy Calculations ◽

Orbital Density

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Substitution Effects on the Optoelectronic Properties of Coumarin Derivatives

Applied Sciences ◽

10.3390/app10010144 ◽

2019 ◽

Vol 10 (1) ◽

pp. 144

Author(s):

Amit Kumar ◽

Roberto Baccoli ◽

Antonella Fais ◽

Alberto Cincotti ◽

Luca Pilia ◽

...

Keyword(s):

Density Functional Theory ◽

Binding Energy ◽

Molecular Orbital ◽

Density Functional ◽

Optoelectronic Properties ◽

Exciton Binding Energy ◽

Basis Set ◽

Substitution Effects ◽

Coumarin Derivatives ◽

Functional Theory

Coumarin derivatives have gathered major attention largely due to their versatile utility in a wide range of applications. In this framework, we report a comparative computational investigation on the optoelectronic properties of 3-phenylcoumarin and 3-heteroarylcoumarin derivatives established as enzyme inhibitors. Specifically, we concentrate on the variation in the optoelectronic characteristics for the hydroxyl group substitutions within the coumarin moiety. In order to realize our aims, all-electron density functional theory and time dependent density functional theory calculations were performed with a localized Gaussian basis-set matched with a hybrid exchange–correlation functionals. Molecular properties such as highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, vertical ionization (IEV) and electron affinity energies, absorption spectra, quasi-particle gap, and exciton binding energy values are examined. Furthermore, the influence of solvent on the optical properties of the molecules is considered. We found a good agreement between the experimental (8.72 eV) and calculated (8.71 eV) IEV energy values for coumarin. The computed exciton binding energy of the investigated molecules indicated their potential optoelectronics application.

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Density Functional Study of H2S Adsorption on Small Agn (n = 1–5)

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.634-638.47 ◽

2013 ◽

Vol 634-638 ◽

pp. 47-51 ◽

Cited By ~ 1

Author(s):

Jun Qing Wen ◽

A Ping Yang ◽

Guo Xiang Chen ◽

Chen Jun Zhang

Keyword(s):

Density Functional Theory ◽

Binding Energy ◽

Density Functional ◽

Global Minimum ◽

Electronic States ◽

Functional Study ◽

Functional Theory ◽

Energy Gaps ◽

Single Fold ◽

Homo And Lumo

The global-minimum geometries and electronic states of AgnH2S (n=1-5) clusters have been calculated using density-functional theory. Our calculations predicate that the stable geometries of AgnH2S clusters can be got by directly adding the H2S molecule on different site of Agn clusters, Agn (n=1-5) clusters would like to bond with sulfur atom and the H2S molecule is partial to hold the top location and single fold coordination site in the clusters. After adsorption, the structures of Agn clusters and H2S molecule keep the original structures and are only distorted slightly. The averaged binding energy reveals that adsorption of H2S molecule can strengthen the stabilities of AgnH2S clusters. The second difference in energy and the energy gaps between the HOMO and LUMO of Agn and AgnH2S have been studied.

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Total atomic binding energy via the density functional theory

International Journal of Quantum Chemistry ◽

10.1002/qua.560320313 ◽

1987 ◽

Vol 32 (3) ◽

pp. 407-408 ◽

Cited By ~ 1

Author(s):

P. Csavinszky

Keyword(s):

Density Functional Theory ◽

Binding Energy ◽

Density Functional ◽

Functional Theory ◽

The Density Functional Theory ◽

Atomic Binding Energy

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Diffusion of Fluorine-Silicon Interstitial Complex in Crystalline Silicon

MRS Proceedings ◽

10.1557/proc-864-e9.1 ◽

2005 ◽

Vol 864 ◽

Author(s):

Scott A. Harrison ◽

Thomas F. Edgar ◽

Gyeong S. Hwang

Keyword(s):

Density Functional Theory ◽

Binding Energy ◽

Charge State ◽

First Principles ◽

Density Functional ◽

Positive Charge ◽

Crystalline Silicon ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

And Diffusion

AbstractBased on first principles density functional theory calculations, we identify the structure and diffusion pathway for a fluorine-silicon interstitial complex (F-Sii). We find the F-Sii complex to be most stable in the singly positive charge state at all Fermi leVels. At mid-gap, the complex is found to have a binding energy of 1.08 eV relative to bond-centered F+ and (110)-split Sii. We find the F-Sii complex has an overall migration barrier of 0.76 eV, which suggests that this complex may play an important role in fluorine diffusion. Our results should lead to more accurate models that describe the behavior of fluorine co-implants crystalline silicon.

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