Special Issue "Theoretical Calculation and Molecular Modeling of Nanomaterials"

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Theory and Simulation of Nanostructures".

Deadline for manuscript submissions: 20 January 2023 | Viewed by 12844

Special Issue Editor

Prof. Dr. Frederik Tielens
E-Mail Website
Guest Editor
General Chemistry (ALGC), Materials Modelling Group, Vrije Universiteit Brussels, 1050 Brussels, Belgium
Interests: density functional theory (DFT); silica-based materials; noble metals; bio- and biological materials; theoretical chemistry; computational chemistry; materials characterization at the atomic/molecular level
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Special Issue Information

Dear Colleagues,

The success of computational chemistry and chemical modeling of materials is in line with the available computation power and techniques, evolving every day. This evolution has kept chemists’ skills in the limelight. Indeed, Moore’s law being respected or not, modeling has now shifted to the creation of the model itself. Of course, the accuracy of calculations can be still be improved, but the main chemical properties and their trends are relatively well reproduced today. One can say that DFT is now at a mature age, and that it can be used as a reliable prediction tool in material science applications. Classical molecular dynamics is indispensable for the study of large systems. Other methods are emerging, though, such as AI-based methods. We are entering an exciting era in which our own creativity will be the limit for understanding our environment—the era of multiscale modeling. In this Special Issue, we want to focus on the construction of pertinent models that can describe and predict, as accurately as possible with the available computation power and techniques, the chemistry of nanomaterials.

Prof. Dr. Frederik Tielens
Guest Editor

Manuscript Submission Information

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Keywords

  • DFT
  • surface science
  • heterogeneous catalysis
  • adsorption
  • electrochemistry
  • solid/liquid interface

Published Papers (11 papers)

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Research

Article
Mechanism for the Intercalation of Aniline Cations into the Interlayers of Graphite
Nanomaterials 2022, 12(14), 2486; https://doi.org/10.3390/nano12142486 - 20 Jul 2022
Viewed by 337
Abstract
The dynamic behaviors of aniline cation (ANI+) intercalating into graphite interlayers are systematically studied by experimental studies and multiscale simulations. The in situ intercalation polymerization designed by response surface methods implies the importance of ultrasonication for achieving the intercalation of ANI [...] Read more.
The dynamic behaviors of aniline cation (ANI+) intercalating into graphite interlayers are systematically studied by experimental studies and multiscale simulations. The in situ intercalation polymerization designed by response surface methods implies the importance of ultrasonication for achieving the intercalation of ANI+. Molecular dynamics and quantum chemical simulations prove the adsorption of ANI+ onto graphite surfaces by cation–π electrostatic interactions, weakening the π–π interactions between graphene layers. The ultrasonication that follows breaks the hydrated ANI+ clusters into individual ANI+. Thus, the released positive charges of these dissociative cations and reduced steric hindrance significantly improve their intercalation ability. With the initial kinetic energy provided by ultrasonic field, the activated ANI+ are able to intercalate into the interlayer of graphite. This work demonstrates the intercalation behaviors of ANI+, which provides an opportunity for investigations regarding organic-molecule-intercalated graphite compounds. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Effect of the Dopant Configuration on the Electronic Transport Properties of Nitrogen-Doped Carbon Nanotubes
Nanomaterials 2022, 12(2), 199; https://doi.org/10.3390/nano12020199 - 07 Jan 2022
Cited by 1 | Viewed by 820
Abstract
Nitrogen-doped carbon nanotubes (N-CNTs) show promise in several applications related to catalysis and electrochemistry. In particular, N-CNTs with a single nitrogen dopant in the unit cell have been extensively studied computationally, but the structure-property correlations between the relative positions of several nitrogen dopants [...] Read more.
Nitrogen-doped carbon nanotubes (N-CNTs) show promise in several applications related to catalysis and electrochemistry. In particular, N-CNTs with a single nitrogen dopant in the unit cell have been extensively studied computationally, but the structure-property correlations between the relative positions of several nitrogen dopants and the electronic transport properties of N-CNTs have not been systematically investigated with accurate hybrid density functional methods. We use hybrid density functional theory and semiclassical Boltzmann transport theory to systematically investigate the effect of different substitutional nitrogen doping configurations on the electrical conductivity of N-CNTs. Our results indicate significant variation in the electrical conductivity and the relative energies of the different dopant configurations. The findings can be utilized in the optimization of electrical transport properties of N-CNTs. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Grand Canonical Monte Carlo Simulations to Determine the Optimal Interlayer Distance of a Graphene Slit-Shaped Pore for Adsorption of Methane, Hydrogen and their Equimolar Mixture
Nanomaterials 2021, 11(10), 2534; https://doi.org/10.3390/nano11102534 - 28 Sep 2021
Cited by 1 | Viewed by 834
Abstract
The adsorption—for separation, storage and transportation—of methane, hydrogen and their mixture is important for a sustainable energy consumption in present-day society. Graphene derivatives have proven to be very promising for such an application, yet for a good design a better understanding of the [...] Read more.
The adsorption—for separation, storage and transportation—of methane, hydrogen and their mixture is important for a sustainable energy consumption in present-day society. Graphene derivatives have proven to be very promising for such an application, yet for a good design a better understanding of the optimal pore size is needed. In this work, grand canonical Monte Carlo simulations, employing Improved Lennard–Jones potentials, are performed to determine the ideal interlayer distance for a slit-shaped graphene pore in a large pressure range. A detailed study of the adsorption behavior of methane, hydrogen and their equimolar mixture in different sizes of graphene pores is obtained through calculation of absolute and excess adsorption isotherms, isosteric heats and the selectivity. Moreover, a molecular picture is provided through z-density profiles at low and high pressure. It is found that an interlayer distance of about twice the van der Waals distance of the adsorbate is recommended to enhance the adsorbing ability. Furthermore, the graphene structures with slit-shaped pores were found to be very capable of adsorbing methane and separating methane from hydrogen in a mixture at reasonable working conditions (300 K and well below 15 atm). Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Electronic Properties of Carbon Nanobelts Predicted by Thermally-Assisted-Occupation DFT
Nanomaterials 2021, 11(9), 2224; https://doi.org/10.3390/nano11092224 - 29 Aug 2021
Cited by 2 | Viewed by 1672
Abstract
Accurate prediction of properties of large-scale multi-reference (MR) electronic systems remains difficult for traditional computational methods (e.g., the Hartree–Fock theory and Kohn–Sham density functional theory (DFT)). Recently, thermally-assisted-occupation (TAO)-DFT has been demonstrated to offer reliable description of electronic properties of various large-scale MR [...] Read more.
Accurate prediction of properties of large-scale multi-reference (MR) electronic systems remains difficult for traditional computational methods (e.g., the Hartree–Fock theory and Kohn–Sham density functional theory (DFT)). Recently, thermally-assisted-occupation (TAO)-DFT has been demonstrated to offer reliable description of electronic properties of various large-scale MR electronic systems. Consequently, in this work, TAO-DFT is used to unlock the electronic properties associated with C-Belt[n] (i.e., the carbon nanobelts containing n fused 12-membered carbon rings). Our calculations show that for all the system sizes reported (n = 4–24), C-Belt[n] have singlet ground states. In general, the larger the size of C-Belt[n], the more pronounced the MR character of ground-state C-Belt[n], as evident from the symmetrized von Neumann entropy and the occupation numbers of active TAO-orbitals. Furthermore, the active TAO-orbitals are delocalized along the circumference of C-Belt[n], as evident from the visualization of active TAO-orbitals. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
In Search of an Efficient Complexing Agent for Oxalates and Phosphates: A Quantum Chemical Study
Nanomaterials 2021, 11(7), 1763; https://doi.org/10.3390/nano11071763 - 06 Jul 2021
Cited by 1 | Viewed by 1199
Abstract
Limiting gastrointestinal oxalate absorption is a promising approach to reduce urinary oxalate excretion in patients with idiopathic and enteric hyperoxaluria. Phosphate binders, that inhibit gastrointestinal absorption of dietary phosphate by the formation of easily excretable insoluble complexes, are commonly used as a treatment [...] Read more.
Limiting gastrointestinal oxalate absorption is a promising approach to reduce urinary oxalate excretion in patients with idiopathic and enteric hyperoxaluria. Phosphate binders, that inhibit gastrointestinal absorption of dietary phosphate by the formation of easily excretable insoluble complexes, are commonly used as a treatment for hyperphosphatemia in patients with end-stage renal disease. Several of these commercially available phosphate binders also have affinity for oxalate. In this work, a series of metallic cations (Li+, Na+, Mg2+, Ca2+, Fe2+, Cu2+, Zn2+, Al3+, Fe3+ and La3+) is investigated on their binding affinity to phosphate and oxalate on one side and anionic species that could be used to administer the cationic species to the body on the other, e.g., acetate, carbonate, chloride, citrate, formate, hydroxide and sulphate. Through quantum chemical calculations, the aim is to understand the competition between the different complexes and propose possible new and more efficient phosphate and oxalate binders. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Surface Energy of Curved Surface Based on Lennard-Jones Potential
Nanomaterials 2021, 11(3), 686; https://doi.org/10.3390/nano11030686 - 09 Mar 2021
Cited by 3 | Viewed by 968
Abstract
Although various phenomena have confirmed that surface geometry has an impact on surface energy at micro/nano scales, determining the surface energy on micro/nano curved surfaces remains a challenge. In this paper, based on Lennard-Jones (L-J) pair potential, we study the geometrical effect on [...] Read more.
Although various phenomena have confirmed that surface geometry has an impact on surface energy at micro/nano scales, determining the surface energy on micro/nano curved surfaces remains a challenge. In this paper, based on Lennard-Jones (L-J) pair potential, we study the geometrical effect on surface energy with the homogenization hypothesis. The surface energy is expressed as a function of local principle curvatures. The accuracy of curvature-based surface energy is confirmed by comparing surface energy on flat surface with experimental results. Furthermore, the surface energy for spherical geometry is investigated and verified by the numerical experiment with errors within 5%. The results show that (i) the surface energy will decrease on a convex surface and increase on a concave surface with the increasing of scales, and tend to the value on flat surface; (ii) the effect of curvatures will be obvious and exceed 5% when spherical radius becomes smaller than 5 nm; (iii) the surface energy varies with curvatures on sinusoidal surfaces, and the normalized surface energy relates with the ratio of wave height to wavelength. The curvature-based surface energy offers new insights into the geometrical and scales effect at micro/nano scales, which provides a theoretical direction for designing NEMS/MEMS. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Molecular Understanding of Electrochemical–Mechanical Responses in Carbon-Coated Silicon Nanotubes during Lithiation
Nanomaterials 2021, 11(3), 564; https://doi.org/10.3390/nano11030564 - 24 Feb 2021
Cited by 2 | Viewed by 906
Abstract
Carbon-coated silicon nanotube ([email protected]) anodes show tremendous potential in high-performance lithium ion batteries (LIBs). Unfortunately, to realize the commercial application, it is still required to further optimize the structural design for better durability and safety. Here, the electrochemical and mechanical evolution in lithiated [...] Read more.
Carbon-coated silicon nanotube ([email protected]) anodes show tremendous potential in high-performance lithium ion batteries (LIBs). Unfortunately, to realize the commercial application, it is still required to further optimize the structural design for better durability and safety. Here, the electrochemical and mechanical evolution in lithiated [email protected] nanohybrids are investigated using large-scale atomistic simulations. More importantly, the lithiation responses of [email protected] nanohybrids are also investigated in the same simulation conditions as references. The simulations quantitatively reveal that the inner hole of the SiNT alleviates the compressive stress concentration between a-LixSi and C phases, resulting in the [email protected] having a higher Li capacity and faster lithiation rate than [email protected] The contact mode significantly regulates the stress distribution at the inner hole surface, further affecting the morphological evolution and structural stability. The inner hole of bare SiNT shows good structural stability due to no stress concentration, while that of concentric [email protected] undergoes dramatic shrinkage due to compressive stress concentration, and that of eccentric [email protected] is deformed due to the mismatch of stress distribution. These findings not only enrich the atomic understanding of the electrochemical–mechanical coupled mechanism in lithiated [email protected] nanohybrids but also provide feasible solutions to optimize the charging strategy and tune the nanostructure of SiNT-based electrode materials. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Atomistic Insights into Aluminum Doping Effect on Surface Roughness of Deposited Ultra-Thin Silver Films
Nanomaterials 2021, 11(1), 158; https://doi.org/10.3390/nano11010158 - 10 Jan 2021
Cited by 2 | Viewed by 1326
Abstract
Ultra-thin and continuous metallic silver films are attracting growing interest due to the applications in flexible transparent conducting electrodes. The surface morphology and structure of silver film are very important for its electrical resistivity and optical loss. Therefore, roughness control is essential for [...] Read more.
Ultra-thin and continuous metallic silver films are attracting growing interest due to the applications in flexible transparent conducting electrodes. The surface morphology and structure of silver film are very important for its electrical resistivity and optical loss. Therefore, roughness control is essential for the production of ultra-thin metallic electrode film. We have investigated the effect of aluminum doping on the improvement of surface morphology of ultra-thin silver films using molecular dynamics simulations. Al-doped silver films showed smaller surface roughness than pure silver films at various substrate temperatures. When the temperature of the substrate was 600 K, the roughness of Al-doped silver film first decreased, and then increased with the increase of the incident velocity of silver atoms. Silver atoms were more likely to agglomerate on the surface of the substrate after adding aluminum atoms, as aluminum dopants promoted the immobilization of silver atoms on SiO2 substrate due to the anchoring effect. The smoother surface could be attributable to the reduced mean free path of silver due to the cage effect by the aluminum dopant. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Exfoliation Energy as a Descriptor of MXenes Synthesizability and Surface Chemical Activity
Nanomaterials 2021, 11(1), 127; https://doi.org/10.3390/nano11010127 - 07 Jan 2021
Cited by 10 | Viewed by 1382
Abstract
MXenes are two-dimensional nanomaterials isolated from MAX phases by selective extraction of the A component—a p-block element. The MAX exfoliation energy, Eexf, is considered a chemical descriptor of the MXene synthesizability. Here, we show, by density functional theory (DFT) estimations [...] Read more.
MXenes are two-dimensional nanomaterials isolated from MAX phases by selective extraction of the A component—a p-block element. The MAX exfoliation energy, Eexf, is considered a chemical descriptor of the MXene synthesizability. Here, we show, by density functional theory (DFT) estimations of Eexf values for 486 different MAX phases, that Eexf decreases (i) when MAX is a nitride, (ii) when going along a metal M component d series, (iii) when going down a p-block A element group, and (iv) when having thicker MXenes. Furthermore, Eexf is found to bias, even to govern, the surface chemical activity, evaluated here on the CO2 adsorption strength, so that more unstable MXenes, displaying larger Eexf values, display a stronger attachment of species upon. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
Heterofullerene MC59 (M = B, Si, Al) as Potential Carriers for Hydroxyurea Drug Delivery
Nanomaterials 2021, 11(1), 115; https://doi.org/10.3390/nano11010115 - 07 Jan 2021
Cited by 7 | Viewed by 808
Abstract
As a representative nanomaterial, C60 and its derivatives have drawn much attention in the field of drug delivery over the past years, due to their unique geometric and electronic structures. Herein, the interactions of hydroxyurea (HU) drug with the pristine C60 [...] Read more.
As a representative nanomaterial, C60 and its derivatives have drawn much attention in the field of drug delivery over the past years, due to their unique geometric and electronic structures. Herein, the interactions of hydroxyurea (HU) drug with the pristine C60 and heterofullerene MC59 (M = B, Si, Al) were investigated using the density functional theory calculations. The geometric and electronic properties in terms of adsorption configuration, adsorption energy, Hirshfeld charge, frontier molecular orbitals, and charge density difference are calculated. In contrast to pristine C60, it is found that HU molecule is chemisorbed on the BC59, SiC59, and AlC59 molecules with moderate adsorption energy and apparent charge transfer. Therefore, heterofullerene BC59, SiC59, and AlC59 are expected to be promising carriers for hydroxyurea drug delivery. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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Article
A Theoretical Study of the Occupied and Unoccupied Electronic Structure of High- and Intermediate-Spin Transition Metal Phthalocyaninato (Pc) Complexes: VPc, CrPc, MnPc, and FePc
Nanomaterials 2021, 11(1), 54; https://doi.org/10.3390/nano11010054 - 28 Dec 2020
Cited by 6 | Viewed by 1554
Abstract
The structural, electronic, and spectroscopic properties of high- and intermediate-spin transition metal phthalocyaninato complexes (MPc; M = V, Cr, Mn and Fe) have been theoretically investigated to look into the origin, symmetry and strength of the M–Pc bonding. DFT calculations coupled to the [...] Read more.
The structural, electronic, and spectroscopic properties of high- and intermediate-spin transition metal phthalocyaninato complexes (MPc; M = V, Cr, Mn and Fe) have been theoretically investigated to look into the origin, symmetry and strength of the M–Pc bonding. DFT calculations coupled to the Ziegler’s extended transition state method and to an advanced charge density and bond order analysis allowed us to assess that the M–Pc bonding is dominated by σ interactions, with FePc having the strongest and most covalent M–Pc bond. According to experimental evidence, the lightest MPcs (VPc and CrPc) have a high-spin ground state (GS), while the MnPc and FePc GS spin is intermediate. Insights into the MPc unoccupied electronic structure have been gained by modelling M L2,3-edges X-ray absorption spectroscopy data from the literature through the exploitation of the current Density Functional Theory variant of the Restricted Open-Shell Configuration Interaction Singles (DFT/ROCIS) method. Besides the overall agreement between theory and experiment, the DFT/ROCIS results indicate that spectral features lying at the lowest excitation energies (EEs) are systematically generated by electronic states having the same GS spin multiplicity and involving M-based single electronic excitations; just as systematically, the L3-edge higher EE region of all the MPcs herein considered includes electronic states generated by metal-to-ligand-charge-transfer transitions involving the lowest-lying π* orbital (7eg) of the phthalocyaninato ligand. Full article
(This article belongs to the Special Issue Theoretical Calculation and Molecular Modeling of Nanomaterials)
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