Search results for "Density functional theory"
showing 10 items of 981 documents
What Contributes to the Measured Chiral Optical Response of the Glutathione-Protected Au25 Nanocluster?
2023
The water-soluble glutathione-protected [Au25(GSH)18]−1 nanocluster was investigated by integrating several methodologies such as molecular dynamics simulations, essential dynamics analysis, and state-of-the-art time-dependent density functional theory calculations. Fundamental aspects such as conformational, weak interactions and solvent effects, especially hydrogen-bonds, were included and found to play a fundamental role in assessing the optical response of this system. Our analysis demonstrated not only that the electronic circular dichroism is extremely sensitive to the solvent presence but also that the solvent itself plays an active role in the optical activity of such system, formin…
B–T phase diagram of Pd/Fe/Ir(111) computed with parallel tempering Monte Carlo
2017
We use an atomistic spin model derived from density functional theory calculations for the ultra-thin film Pd/Fe/Ir(111) to show that temperature induces coexisting non-zero skyrmion and antiskyrmion densities. We apply the parallel tempering Monte Carlo method in order to reliably compute thermodynamical quantities and the B-T phase diagram in the presence of frustrated exchange interactions. We evaluate the critical temperatures using the topological susceptibility. We show that the critical temperatures depend on the magnetic field in contrast to previous work. In total, we identify five phases: spin spiral, skyrmion lattice, ferromagnetic phase, intermediate region with finite topologic…
Pullout Force and Inlet Oscillation in Telescopic Carbon Nanotubes: A Quantum Study
2021
The noncovalent interaction energy as a function of the core extension in double-walled carbon nanotubes (DWCNT) was accurately calculated in the frame of density functional theory, considering dis...
Escaping scaling relationships for water dissociation at interfacial sites of zirconia-supported Rh and Pt clusters
2019
<p>Water dissociation is an important reaction involved in many industrial processes and a good model reaction for probing the activity of catalytic sites. In this computational study, the dissociation of water at interfacial sites of globally optimized ZrO2 sup- ported Pt and Rh clusters is investigated under the framework of density functional theory. Our findings demonstrate that the perimeter sites of these small clusters can activate water, but the dissociation behavior varies considerably between sites. It is shown that the studied clusters break scaling relationships for water dissociation, suggesting these catalysts may achieve activities beyond the maximum imposed by such rel…
A Computational Study of Adsorption of CO2, SO2, and H2CO on Free-Standing and Molybdenum-Supported CaO Films
2018
Oxide films play a significant role in a wide range of fields from catalysis to solar cell materials. CaO films are promising sorbents for many environmentally harmful molecules. Here, we report a systematic investigation of adsorption of CO2, SO2, and H2CO on bulk and Mo-supported CaO(100) films using density functional theory. Significant effects on adsorption energy, charge transfer to the molecules, and degree of the C–O bond activation were demonstrated on Mo-supported CaO films by changing the film thickness, composition, and the strength and direction of an applied external electric field. These findings are relevant for interpreting results from scanning tunneling microscopy of smal…
Influence of a Cu–zirconia interface structure on CO2 adsorption and activation
2021
CO2 adsorption and activation on a catalyst are key elementary steps for CO2 conversion to various valuable products. In the present computational study, we screened different Cu–ZrO2 interface structures and analyzed the influence of the interface structure on CO2 binding strength using density functional theory calculations. Our results demonstrate that a Cu nanorod favors one position on both tetragonal and monoclinic ZrO2 surfaces, where the bottom Cu atoms are placed close to the lattice oxygens. In agreement with previous calculations, we find that CO2 prefers a bent bidentate configuration at the Cu–ZrO2 interface and the molecule is clearly activated being negatively charged. Strain…
ReO as a Brønsted acidic modifier in glycerol hydrodeoxygenation : Computational insight into the balance between acid and metal catalysis
2023
A computational study for the competitive conversion of glycerol to 1,2-propanediol and 1,3-propanediol is presented, considering a two-step sequence of dehydration followed by hydrogenation. The elementary steps for dehydration, i.e., breaking of C–H followed by C–OH or vice versa, were studied computationally both on the Rh metal surface and the acid-modified ReOH–Rh surface in order to understand the role of the acid promoter. While the acid modifier can catalyze the C–OH cleavage, the activation energy for the C–H cleavage was found to be considerably smaller on both pure and acid-doped Rh(111) surfaces, and breaking the secondary C–H bond is kinetically favored over breaking the termin…
Self-Assembled Molecular Rafts at Liquid|Liquid Interfaces for Four-Electron Oxygen Reduction
2011
The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning …
Atomic Layer Deposition of Aluminum Oxide on TiO2 and Its Impact on N3 Dye Adsorption from First Principles
2011
The atomic layer deposition of aluminum oxide on an OH-terminated TiO2(101) anatase surface was studied employing density functional theory calculations. The formation of the Al2O3−TiO2 interface during the first atomic layer deposition cycle was modeled by studying the dissociative adsorption of an Al(CH3)3 precursor, followed with a H2O-pulse reaction step that changes the surface termination. Calculations provide evidence for the formation of a discontinuous, atomically rough aluminum oxide layer after the first cycle. To explore the role of the aluminum oxide layer on adsorption of a ruthenium-based N3 dye molecule, various adsorption geometries were investigated. Calculations show that…
DFT modelling of oxygen adsorption on the Ag-doped LaMnO3 (001) surface
2019
This study was partly financed by the State Education Development Agency of the Republic of Latvia via the Latvian State Scholarship (A.A.) and Latvia-Ukraine Project (Grant LV-UA/2018/2 to E.K.). The work of T.I. is performed under the state assignment of IGM SB RAS. Also, this research was partly supported by the Ministry of Education and Science of the Republic of Kazakhstan in the framework of the scientific and technology Program BR05236795 ‘‘Development of Hydrogen Energy Technologies in the Republic of Kazakhstan’’. The authors thank M. Sokolov for technical assistance and valuable suggestions.