Effects of Solvents on Adsorption Energies: A General Bond-Additivity Model

2021 ◽  
Author(s):  
James Akinola ◽  
Charles T. Campbell ◽  
Nirala Singh
Keyword(s):  
Adsorption Energies

Scalable Approach to High Coverages on Oxides via Iterative Training of a Machine-Learning Algorithm

2019 ◽  
Author(s):  
Andrew Medford ◽  
Shengchun Yang ◽  
Fuzhu Liu
Keyword(s):  
Machine Learning ◽  
Chemical Potential ◽  
Learning Algorithm ◽  
Absolute Error ◽  
Low Energy ◽  
Training Data ◽  
High Coverage ◽  
Metal Compounds ◽  
Adsorption Energies ◽  
The Stability

Understanding the interaction of multiple types of adsorbate molecules on solid surfaces is crucial to establishing the stability of catalysts under various chemical environments. Computational studies on the high coverage and mixed coverages of reaction intermediates are still challenging, especially for transition-metal compounds. In this work, we present a framework to predict differential adsorption energies and identify low-energy structures under high- and mixed-adsorbate coverages on oxide materials. The approach uses Gaussian process machine-learning models with quantified uncertainty in conjunction with an iterative training algorithm to actively identify the training set. The framework is demonstrated for the mixed adsorption of CH<sub>x</sub>, NH<sub>x</sub> and OH<sub>x</sub> species on the oxygen vacancy and pristine rutile TiO<sub>2</sub>(110) surface sites. The results indicate that the proposed algorithm is highly efficient at identifying the most valuable training data, and is able to predict differential adsorption energies with a mean absolute error of ~0.3 eV based on <25% of the total DFT data. The algorithm is also used to identify 76% of the low-energy structures based on <30% of the total DFT data, enabling construction of surface phase diagrams that account for high and mixed coverage as a function of the chemical potential of C, H, O, and N. Furthermore, the computational scaling indicates the algorithm scales nearly linearly (N<sup>1.12</sup>) as the number of adsorbates increases. This framework can be directly extended to metals, metal oxides, and other materials, providing a practical route toward the investigation of the behavior of catalysts under high-coverage conditions.

Adsorption on heterogeneous surfaces: Numerical analysis of models for the Dubinin-Radushkevich equation

1981 ◽  
Vol 46 (8) ◽  
pp. 1709-1721 ◽  
Author(s):  
Miloš Smutek ◽  
Arnošt Zukal
Keyword(s):  
Integral Equation ◽  
Numerical Analysis ◽  
Numerical Method ◽  
Adsorption Behaviour ◽  
Heterogeneous Surfaces ◽  
Strong Energy ◽  
Adsorption On Heterogeneous Surfaces ◽  
Heterogeneity Parameter ◽  
Adsorption Energies ◽  
Mobile Adsorption

A numerical method, based on the integral equation of the adsorption on energy heterogeneous surfaces, is suggested for the evaluation of overall isotherm. It is shown that for the distribution of adsorption energies given by Eq. (1.11) and different models of the adsorption behaviour, the overall isotherms obey approximately the Dubinin-Radushkevich equation. The strong energy heterogeneity smears effectively the differences between the localized and mobile adsorption and leads to the same character of the overall isotherm with only a slightly changed heterogeneity parameter.

scholarly journals Templated quasicrystalline ordering of single elements and molecules

2014 ◽  
Vol 70 (a1) ◽  
pp. C81-C81
Author(s):  
H. R. Sharma ◽  
J. A. Smerdon ◽  
K. Nozawa ◽  
K. M. Young ◽  
T. P. Yadav ◽  
...  
Keyword(s):  
Substrate Surface ◽  
Chemical Properties ◽  
Scanning Tunneling ◽  
Three Dimension ◽  
Tunneling Microscopy ◽  
Quantum Size ◽  
Adsorption Energies ◽  
Molecular Layers ◽  
Physical And Chemical ◽  
The Impact

We have used quasicrystals as templates for the exploration of new epitaxial phenomena. Several interesting results have been observed in the growth on surfaces of the common Al-based quasicrystals [1]. These include pseudomorphic monolayers, quasiperiodically modulated multilayer structures, and fivefold-twinned islands with magic heights influenced by quantum size effects [1]. Here we present our recent works on the growth of various elements and molecules on a new substrate, icosahedral (i) Ag-In-Yb quasicrystal, which have resulted in various epitaxial phenomena not observed previously. The growth of Pb on the five-fold surface of i-Ag-In-Yb yields a film which possesses quasicrystalline ordering in three-dimension [2]. Using scanning tunneling microscopy (STM) and DFT calculations of adsorption energies, we find that lead atoms occupy the positions of atoms in the rhombic triacontahedral (RTH) cluster, the building block of the substrate, and thus grow in layers with different heights and adsorption energies. The adlayer–adlayer interaction is crucial for stabilizing the epitaxial quasicrystalline structure. We will also present the first example of quasicrystalline molecular layers. Pentacene adsorbs at tenfold-symmetric sites of Yb atoms around surface-bisected RTH clusters, yielding quasicrystalline order [3]. Similarly, C-60 growth on the five-fold surface of i-Al-Cu-Fe at elevated temperature produces quasicrystalline layer, where the growth is mediated by Fe atoms on the substrate surface [3]. The finding of quasicrystalline thin films of single elements and molecules opens an avenue for further investigation of the impact of the aperiodic atomic order over periodic order on the physical and chemical properties of materials.

DFT and Microkinetic Study of Acetylene Transformation on Pd(111), M(111) and PdM(111) Surfaces (M=Cu, Ag, Au)

2021 ◽  
Author(s):  
YUGAI HUANG ◽  
Hui-Li Lu ◽  
Zhao-Xu Chen
Keyword(s):  
Density Functional Calculations ◽  
Density Functional ◽  
Adsorption Energies

Density functional calculations and microkinetic simulations were performed the transformation network of acetylene on Pd(111), M(111) and PdM(111) (M=Cu, Ag, Au) surfaces. It is demonstrated that the adsorption energies on...

scholarly journals Nitrile versus isonitrile adsorption at interstellar grain surfaces

2017 ◽  
Vol 608 ◽  
pp. A50 ◽  
Author(s):  
M. Bertin ◽  
M. Doronin ◽  
X. Michaut ◽  
L. Philippe ◽  
A. Markovits ◽  
...  
Keyword(s):  
Density Functional ◽  
Surface Defects ◽  
High Vacuum ◽  
Solid Support ◽  
Ultra High Vacuum ◽  
Structural Defects ◽  
Adsorption Energies ◽  
The Difference ◽  
Temperature Programmed ◽  
Open Question

Context. Almost 20% of the ~200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims. In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods. The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results. The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

CH2O Adsorption on M (M = Li, Mg and Al) Atom Deposited ZnO Nano-Cage: DFT Study

2018 ◽  
Vol 786 ◽  
pp. 384-392 ◽  
Author(s):  
Hussein Y. Ammar
Keyword(s):  
Density Functional Theory ◽  
Bond Length ◽  
Density Functional ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Structural And Electronic Properties ◽  
Formaldehyde Molecule ◽  
Electronic Configurations ◽  
Adsorption Energies ◽  
Homo Lumo

The structural and electronic properties of Li, Mg and Al deposited ZnO nanocages and their effects on the adsorption of formaldehyde molecule have been investigated using the density functional theory (DFT) computations. To understand the behavior of the adsorbed CH2O molecule on the ZnO nanocage, results of DFT calculations of the M-deposited nanocages (M=Li, Mg and Al), as well as complex systems consisting of the adsorbed CH2O molecule on M-deposited ZnO nanocage were reported. The results presented include adsorption energies, bond lengths, electronic configurations, density of states and molecular orbitals. It was found that, the most energetically stable adsorption configurations of CH2O molecule on the bare ZnO leads to 12% dilation in C=O bond length of CH2O and 14% decrease in HOMO-LUMO gap of ZnO cluster. The most energetically stable adsorption configurations of CH2O molecule on Li, Mg and Al-deposited ZnO lead to 4%, 4% and 11% dilation in C=O bond length of CH2O and-0.66, -45 and , +66% change in HOMO-LUMO gap of ZnO nanocages, respectively. The interaction between CH2O with bare ZnO and M-deposited ZnO nanocages is attributed to charge transfer mechanism. These results may be meaningful for CH2O degradation and detection.

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