Special Issue "First-Principles SimulationNano-Theory"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Inorganic Crystalline Materials".

Deadline for manuscript submissions: closed (20 June 2021).

Special Issue Editors

Dr. Tomoyuki Hamada
E-Mail Website
Guest Editor
International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba, Japan
Interests: Development of first-principles simulation theory and program; high-performance first-principles simulation of condensed matters and molecules
Dr. Paolo Restuccia
E-Mail Website
Guest Editor
Department of Chemistry and Institute for Molecular Science and Engineering, Imperial College London, White City Campus, 80 Wood Lane, London W12 0BZ, UK
Interests: tribology; corrosion; first principles calculations; density functional theory; molecular dynamics; 2D materials; graphene
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

First-principles calculation is the most powerful theoretical tool for investigating the atomistic structure of materials. Today, it is being used as a standard tool of material research covering several branches of science and technology, such as atomic and molecular sciences, pharmacy, polymer chemistry and physics, condensed matter physics minerology, and nanotechnology. First-principles calculation is based on quantum mechanics, which was established in 1930s but is still undergoing evolution, thanks to the rapid development of supercomputers and new theories for the treatment of numerous electron systems at the desired accuracy and within reasonable computation times. First-principles calculation is rapidly broadening its application fields and enabling study of several kinds of material and nanostructure which, until recently, had been impossible to simulate. 

We invite researchers to contribute to the Special Issue “First-Principles Simulation—Nano-Theory”, which intends to serve as a unique multidisciplinary forum covering broad aspects of the science, technology, and applications of first-principles simulations.

The potential topics include, but are not limited to:

- New theory of first-principles simulation

- Development of first-principles calculation code

- Computer science of first-principles calculation

- Simulation of molecules, solid, condensed matter, mineral, surface, and nanostructure

- Simulation of nanodevice

- Simulation of soft matter

- Chemical and pharmaceutical application of first-principles simulation

Dr. Tomoyuki Hamada
Dr. Paolo Restuccia
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • first-principles simulation, theory, program
  • computer science
  • material and device research

Published Papers (12 papers)

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Editorial

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Editorial
First-Principles Simulation—Nano-Theory
Crystals 2021, 11(8), 855; https://doi.org/10.3390/cryst11080855 - 23 Jul 2021
Viewed by 543
Abstract
First-principles (or ab initio) simulation is one of the most significant theoretical approaches to study and model systems at the atomistic level [...] Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)

Research

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Article
High-Throughput Computation of New Carbon Allotropes with Diverse Hybridization and Ultrahigh Hardness
Crystals 2021, 11(7), 783; https://doi.org/10.3390/cryst11070783 - 05 Jul 2021
Cited by 2 | Viewed by 613
Abstract
The discovery of new carbon allotropes with different building blocks and crystal symmetries has long been of great interest to broad materials science fields. Herein, we report several hundred new carbon allotropes predicted by the state-of-the-art RG2 code and first-principles calculations. The [...] Read more.
The discovery of new carbon allotropes with different building blocks and crystal symmetries has long been of great interest to broad materials science fields. Herein, we report several hundred new carbon allotropes predicted by the state-of-the-art RG2 code and first-principles calculations. The types of new carbon allotropes that were identified in this work span pure sp2, hybrid sp2/sp3, and pure sp3 C–C bonding. All structures were globally optimized at the first-principles level. The thermodynamic stability of some selected carbon allotropes was further validated by computing their phonon dispersions. The predicted carbon allotropes possess a broad range of Vickers’ hardness. This wide range of Vickers’ hardness is explained in detail in terms of both atomic descriptors such as density, volume per atom, packing fraction, and local potential energy throughout the unit cell, and global descriptors such as elastic modulus, shear modulus, and bulk modulus, universal anisotropy, Pugh’s ratio, and Poisson’s ratio. For the first time, we found strong correlation between Vickers’ hardness and average local potentials in the unit cell. This work provides deep insight into the identification of novel carbon materials with high Vickers’ hardness for modern applications in which ultrahigh hardness is desired. Moreover, the local potential averaged over the entire unit cell of an atomic structure, an easy-to-evaluate atomic descriptor, could serve as a new atomic descriptor for efficient screening of the mechanical properties of unexplored structures in future high-throughput computing and artificial-intelligence-accelerated materials discovery methods. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
Studies of Hydrogen Bond Vibrations of Hydrogen-Disordered Ice Ic
Crystals 2021, 11(6), 668; https://doi.org/10.3390/cryst11060668 - 10 Jun 2021
Cited by 2 | Viewed by 670
Abstract
The hydrogen-disordered structure of ice, Ic, makes it difficult to analyze the vibrational normal modes in the far-infrared region (i.e., the molecular translation band). To clarify the origin of the energy-splitting of hydrogen bond vibrations in this area, a 64-molecule supercell was constructed [...] Read more.
The hydrogen-disordered structure of ice, Ic, makes it difficult to analyze the vibrational normal modes in the far-infrared region (i.e., the molecular translation band). To clarify the origin of the energy-splitting of hydrogen bond vibrations in this area, a 64-molecule supercell was constructed and calculated using first-principles density functional theory. The results were in good agreement with inelastic neutron scattering experiments and our previous study of a hydrogen-ordered ice Ic model. Assisted by analytic equations, we concluded that the origin of the two hydrogen bond peaks in real ice Ic is consistent with that of hydrogen-ordered ice Ic: the peaks originate from two kinds of normal mode vibration. We categorize the four peaks in the far-infrared region recorded from inelastic neutron scattering experiments as the acoustic peak, the superposition peak, the two-hydrogen bond peak and the four-hydrogen bond peak. We conclude that the existence of two intrinsic hydrogen bond vibration modes represents a general rule among the ice family, except ice X. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
DFT Study of Electronic Structure and Optical Properties of Kaolinite, Muscovite, and Montmorillonite
Crystals 2021, 11(6), 618; https://doi.org/10.3390/cryst11060618 - 30 May 2021
Cited by 1 | Viewed by 910
Abstract
Clay mineral materials have attracted attention due to their many properties and applications. The applications of clay minerals are closely linked to their structure and composition. In this paper, we studied the electronic structure properties of kaolinite, muscovite, and montmorillonite crystals, which are [...] Read more.
Clay mineral materials have attracted attention due to their many properties and applications. The applications of clay minerals are closely linked to their structure and composition. In this paper, we studied the electronic structure properties of kaolinite, muscovite, and montmorillonite crystals, which are classified as clay minerals, by using DFT-based ab initio packages VASP and the OLCAO. The aim of this work is to have a deep understanding of clay mineral materials, including electronic structure, bond strength, mechanical properties, and optical properties. It is worth mentioning that understanding these properties may help continually result in new and innovative clay products in several applications, such as in pharmaceutical applications using kaolinite for their potential in cancer treatment, muscovite used as insulators in electrical appliances, and engineering applications that use montmorillonite as a sealant. In addition, our results show that the role played by hydrogen bonds in O-H bonds has an impact on the hydration in these crystals. Based on calculated total bond order density, it is concluded that kaolinite is slightly more cohesive than montmorillonite, which is consistent with the calculated mechanical properties. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
A Computational Validation of Water Molecules Adsorption on an NaCl Surface
Crystals 2021, 11(6), 610; https://doi.org/10.3390/cryst11060610 - 28 May 2021
Cited by 1 | Viewed by 824
Abstract
It was reported that a scanning tunneling microscopy (STM) study observed the adsorption geometry of a water monomer and a tetramer on NaCl(100) film. Based on first-principles density functional theory (DFT), the adsorption behavior of water on the NaCl surface was simulated with [...] Read more.
It was reported that a scanning tunneling microscopy (STM) study observed the adsorption geometry of a water monomer and a tetramer on NaCl(100) film. Based on first-principles density functional theory (DFT), the adsorption behavior of water on the NaCl surface was simulated with CASTEP code. The results showed that the water monomer almost lay on the NaCl(001) surface with one O–H bond tilted slightly downward. This was quite different from the STM observations. In fact, the experimental observation was influenced by the Au(111) substrate, which showed an upright form. A recent report on observations of two-dimensional ice structure on Au(111) substrate verified our simulations. However, the water tetramer formed a stable quadrate structure on the surface, which was consistent with observation. The intermolecular hydrogen bonds present more strength than surface adsorption. The simulations presented a clearer picture than experimental observations. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
Electrical Breakdown Mechanism of Transformer Oil with Water Impurity: Molecular Dynamics Simulations and First-Principles Calculations
Crystals 2021, 11(2), 123; https://doi.org/10.3390/cryst11020123 - 27 Jan 2021
Cited by 1 | Viewed by 592
Abstract
Water impurity is the essential factor of reducing the insulation performance of transformer oil, which directly determines the operating safety and life of a transformer. Molecular dynamics simulations and first-principles electronic-structure calculations are employed to study the diffusion behavior of water molecules and [...] Read more.
Water impurity is the essential factor of reducing the insulation performance of transformer oil, which directly determines the operating safety and life of a transformer. Molecular dynamics simulations and first-principles electronic-structure calculations are employed to study the diffusion behavior of water molecules and the electrical breakdown mechanism of transformer oil containing water impurities. The molecular dynamics of an oil-water micro-system model demonstrates that the increase of aging acid concentration will exponentially expedite thermal diffusion of water molecules. Density of states (DOS) for a local region model of transformer oil containing water molecules indicates that water molecules can introduce unoccupied localized electron-states with energy levels close to the conduction band minimum of transformer oil, which makes water molecules capable of capturing electrons and transforming them into water ions during thermal diffusion. Subsequently, under a high electric field, water ions collide and impact on oil molecules to break the molecular chain of transformer oil, engendering carbonized components that introduce a conduction electronic-band in the band-gap of oil molecules as a manifestation of forming a conductive region in transformer oil. The conduction channel composed of carbonized components will be eventually formed, connecting two electrodes, with the carbonized components developing rapidly under the impact of water ions, based on which a large number of electron carriers will be produced similar to “avalanche” discharge, leading to an electrical breakdown of transformer oil insulation. The water impurity in oil, as the key factor for forming the carbonized conducting channel, initiates the electric breakdown process of transformer oil, which is dominated by thermal diffusion of water molecules. The increase of aging acid concentration will significantly promote the thermal diffusion of water impurities and the formation of an initial conducting channel, accounting for the degradation in dielectric strength of insulating oil containing water impurities after long-term operation of the transformer. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
First Principle Analysis on Pyridine Amide Derivatives’ Adsorption Behavior on the Pt (111) Surface
Crystals 2021, 11(2), 98; https://doi.org/10.3390/cryst11020098 - 24 Jan 2021
Cited by 2 | Viewed by 769
Abstract
The reactivity and adsorption behavior of three pyridine amide additives (Nicotinamide, Pyridine-2-formamide and Pyridine-4-formamide) on the Pt (111) surface was studied by First principle methods. The quantum chemical calculations of molecular reactivity show that the frontier orbitals of the three additives are distributed [...] Read more.
The reactivity and adsorption behavior of three pyridine amide additives (Nicotinamide, Pyridine-2-formamide and Pyridine-4-formamide) on the Pt (111) surface was studied by First principle methods. The quantum chemical calculations of molecular reactivity show that the frontier orbitals of the three additives are distributed around the pyridine ring, oxygen atom of carbonyl and nitrogen atom of amino, and the nucleophilic and electrophilic active centers are located on the nitrogen atoms of pyridine ring, oxygen atom of carbonyl and nitrogen atom of amino. All three molecules were adsorbed with the chemical adsorption on the Pt (111) surface, and the order of adsorption was Nicotinamide > Pyridine-2-formamide > Pyridine-4-formamide. The C and N atoms of three derivatives forms C-Pt and N-Pt bonds with the Pt atoms of the Pt (111) surface, which makes derivatives stably adsorb on the Pt surface and form a protective film. The protective film inhibits the diffusion of atoms to the surface of the growth center, so as to inhibit the formation of dendrite and obtain a smooth aluminum deposition layer. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
Modulation Effect of Hardness on the Friction Coefficient and Its Mechanism Analysis of ZrB2/Mo Multilayers Synthesized by Magnetron Sputtering
Crystals 2021, 11(1), 69; https://doi.org/10.3390/cryst11010069 - 16 Jan 2021
Cited by 1 | Viewed by 597
Abstract
ZrB2/Mo multilayers were prepared by the magnetron sputtering technique on Si (100) and Al2O3 (001) substrates. The friction behavior and wear mechanism of the multilayers were tested at variable modulation ratios (tZrB2:tMo) [...] Read more.
ZrB2/Mo multilayers were prepared by the magnetron sputtering technique on Si (100) and Al2O3 (001) substrates. The friction behavior and wear mechanism of the multilayers were tested at variable modulation ratios (tZrB2:tMo) of 1:1 to 8:1 at different temperatures. Under the influence of an effective modulation ratio and temperature, the friction coefficient and hardness of ZrB2/Mo multilayers showed an almost opposite change rule, that is, the higher the hardness, the lower the friction coefficient. The hardness and elastic modulus reached the maximum value (26.1 GPa and 241.99 GPa) at tZrB2:tMo = 5:1 and the corresponding friction coefficient was 0.86. Meanwhile, the hardness and average friction coefficient at 500 °C were, respectively, 8.9 GPa and 1.23. First-principles calculations of the interface model of ZrB2 (001)/Mo (110) showed that the ionic bonds and covalent bonds at the interface can effectively improve the viscosity of the multilayer and the stability of the interface, and thus increase the hardness. This also indicated that the variation of the friction coefficient was mainly determined by the stability of the interface in the ZrB2/Mo multilayers. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
First-Principles Study on Redox Magnetism and Electrochromism of Cyclometalated Triarylamine-Core Triruthenium Complex
Crystals 2021, 11(1), 57; https://doi.org/10.3390/cryst11010057 - 13 Jan 2021
Cited by 1 | Viewed by 564
Abstract
Spin electronic states and optical properties of a circular ruthenium (Ru) terpyridine complex with a triarylamine core (CTTC) are theoretically investigated by first-principles calculations within an all-electron numerical orbital scheme based on spin density functional theory (SDFT), which demonstrate five well-defined redox states [...] Read more.
Spin electronic states and optical properties of a circular ruthenium (Ru) terpyridine complex with a triarylamine core (CTTC) are theoretically investigated by first-principles calculations within an all-electron numerical orbital scheme based on spin density functional theory (SDFT), which demonstrate five well-defined redox states for electrochromic functions. Atomic structure of CTTC molecule is obtained by geometric optimization, and its electronic structure with a decreasing semiconductor band-gap exhibits five consecutive single-electron redox states of Ru-coordinated centers. Except for CTTC in (Ru)3+4 redox state exhibiting a net spin of 2.25 (ћ/2), the other redox states are almost zero in total spin. Density distribution and energy-splitting of spin states indicate that the ferromagnetic coupling of Ru cations coordinating with terpyridine/triarylamine ligands originates dominantly from the spin polarization of Ru 4d-orbitals coordinated by N- and C-2p electrons of triarylamine. CTTC molecule in each redox state represents a well-discriminated absorption in visible region, with the highest characteristic peaks locating at 24.2, 20.2, 21.3, and 19.3/21.7 (103 cm−1) and a manifold of peaks at 13.4~25.3 (103 cm−1) for +2~+6 redox states, respectively. Theoretical electronic structure and optics of CTTC complex are used to evaluate the underlying physical mechanism of realizing a multi-color visible electrochromism by four couples of redox pairs, which is suggested to be applied for monitoring electrical information. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
Optoelectronic Properties of Ultrathin Indium Tin Oxide Films: A First-Principle Study
Crystals 2021, 11(1), 30; https://doi.org/10.3390/cryst11010030 - 30 Dec 2020
Cited by 1 | Viewed by 763
Abstract
First-principle density functional theory simulations have been performed to predict the electronic structures and optoelectronic properties of ultrathin indium tin oxide (ITO) films, having different thicknesses and temperatures. Our results and analysis led us to predict that the physical properties of ultrathin films [...] Read more.
First-principle density functional theory simulations have been performed to predict the electronic structures and optoelectronic properties of ultrathin indium tin oxide (ITO) films, having different thicknesses and temperatures. Our results and analysis led us to predict that the physical properties of ultrathin films of ITO have a direct relation with film thickness rather than temperature. Moreover, we found that a thin film of ITO (1 nm thickness) has a larger absorption coefficient, lower reflectivity, and higher transmittance in the visible light region compared with that of 2 and 3 nm thick ITO films. We suggest that this might be due to the stronger surface strain effect in 1 nm thick ITO film. On the other hand, all three thin films produce similar optical spectra. Finally, excellent agreement was found between the calculated electrical resistivities of the ultrathin film of ITO and that of its experimental data. It is concluded that the electrical resistivities reduce along with the increase in film thickness of ITO because of the short strain length and limited bandgap distributions. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
First-Principles Electronic-Structure Study of Graphene Decorated with 4d-Transition Atoms
Crystals 2021, 11(1), 29; https://doi.org/10.3390/cryst11010029 - 30 Dec 2020
Cited by 2 | Viewed by 593
Abstract
Adsorption configurations, electronic structures and net spins of graphene adsorbing 4d transition atoms are calculated by first-principles calculations to explore the magnetic modification of decorating metal atoms on graphene. Y, Zr and Nb atoms can be adsorbed on graphene sheet via ionic [...] Read more.
Adsorption configurations, electronic structures and net spins of graphene adsorbing 4d transition atoms are calculated by first-principles calculations to explore the magnetic modification of decorating metal atoms on graphene. Y, Zr and Nb atoms can be adsorbed on graphene sheet via ionic bonds with an evident charge transfer, while Mo, Tc, Ru and Rh atoms form covalent-like bonding with graphene carbon atoms due to orbital hybridization, as indicated by Mulliken atomic charges and electron density differences. The 4d-transition atoms can be adsorbed on a carbon-ring center and atomic-bridge with a high binding energy as the typical chemisorption, which leads to specific modifications in electronic-band character and magnetic properties by introducing electron-states near Fermi-level. By adsorbing 4d-transition atoms, the electronic structure of graphene will alter from a semi-metal to a metal character, and engender net spin magnetism from the spin-polarization in 5s and 4d orbitals of adsorption atoms. This paper provides a significant theoretical basis for further experimental explorations of the atom-decorated graphene in nanoelectronics. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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Article
The Study on Structural and Photoelectric Properties of Zincblende InGaN via First Principles Calculation
Crystals 2020, 10(12), 1159; https://doi.org/10.3390/cryst10121159 - 19 Dec 2020
Cited by 3 | Viewed by 654
Abstract
In this paper, the structure and photoelectric characteristics of zincblende InxGa1−xN alloys are systematically calculated and analyzed based on the density functional theory, including the lattice constant, band structure, distribution of electronic states, dielectric function, and absorption coefficient. [...] Read more.
In this paper, the structure and photoelectric characteristics of zincblende InxGa1−xN alloys are systematically calculated and analyzed based on the density functional theory, including the lattice constant, band structure, distribution of electronic states, dielectric function, and absorption coefficient. The calculation results show that with the increase in x, the lattice constants and the supercell volume increase, whereas the bandgap tends to decrease, and InxGa1−xN alloys are direct band gap semiconductor materials. In addition, the imaginary part of the dielectric function and the absorption coefficient are found to redshift with the increase in indium composition, expanding the absorption range of visible light. By analyzing the lattice constants, polarization characteristics, and photoelectric properties of the InxGa1−xN systems, it is observed that zincblende InxGa1−xN can be used as an alternative material to replace the channel layer of wurtzite InxGa1−xN heterojunction high electron mobility transistor (HEMT) devices to achieve the manufacture of HEMT devices with higher power and higher frequency. In addition, it also provides a theoretical reference for the practical application of InxGa1−xN systems in optoelectronic devices. Full article
(This article belongs to the Special Issue First-Principles SimulationNano-Theory)
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