Computational Investigation on Cr-Doped Sc2CO2 MXene under Strain for Electronic Properties, Quantum Capacitance, and Photocatalytic Activity.

Sc2CO2 MXene has potential applications in energy storage and optoelectronics due to its superior structure and excellent properties. The electronic properties, quantum capacitance, and photocatalytic activity of Cr-doped Sc2CO2 under strain are studied by the density functional theory. Cr doping makes the system produce magnetism. The spin-down states of Sc2CO2-Cr under strain are direct semiconductors, while their spin-up states are indirect semiconductors. Sc2CO2-Cr under +5, -5, -3, and -2% strains in an aqueous system are suitable for cathode material. A large voltage drastically modulates the type of electrode materials. Sc2CO2-Cr under strains from 0 to +2% can perform the oxygen evolution reaction at an alkaline environment, while the Sc2CO2-Cr system under strain is a good for CO2 photocatalysis at pH 0 and 7.

Regulating the electronic properties, quantum capacitance and photocatalytic activity of Sc2CO2 based on Y doping and strain.

The doping of transition metals can effectively modulate the electronic structures and enhance the photocatalytic activity of MXenes. The electronic and photocatalytic properties, as well as the quantum capacitance of Sc2CO2-Y under biaxial strain, were studied by density functional theory. Sc2CO2-Y is a direct semiconductor and keeps its semiconductor character under strain. Sc2CO2-Y under tensile strain has higher photocatalytic activity than under compressive strain. In particular, Sc2CO2-Y at 2% strain has the slowest recombination rate of electrons and holes because of the largest . Sc2CO2-Y under strain is a potential cathode material. Its large potential keeps the character of cathode materials for Sc2CO2-Y under strain. Sc2CO2-Y under tensile strain has better conductivity, especially under 5% strain, due to having the largest Re (ε0). Sc2CO2-Y under strain can perform the HER, but fails to perform the OER at pH = 0, and tensile strain increases the reduction capacity of Sc2CO2-Y. Under strains from -2% to 2%, Sc2CO2-Y can perform the OER in an alkaline environment. Sc2CO2-Y is a good CO2 photocatalyst in acidic environments; the increase of pH value weakens the N2 reducing capacity of Sc2CO2-Y under strain. Its work function, charge transfer and optical properties are also explored.

A predicted orthogonal semimetallic carbon with negative thermal expansion and compressibility.

Carbon has many allotropes possessing unique properties. In this work, we predicted an orthogonal carbon crystal, named ort-C24, with dynamic, mechanical and thermodynamic stability. Studies indicate that it is a topological semimetal having both nodal rings and nodal lines in its Brillouin zone. Ab initio molecular dynamics simulations reveal that it is a rare material having a negative thermal expansion coefficient along the a axis. It also has negative compressibility along the same axis under hydrostatic pressure. Its b axis can bear an astonishing strain of 115% even if the dynamical stability is considered. Tensioning along different axes can either change it into a metal or alter the nodal ring into nodal lines or only modify the shape of the nodal ring, together with the variation of the number of Dirac cones. Theoretically, temperature has a limited influence on its electronic topological properties while a hydrostatic pressure of 5 GPa can alter it noticeably. The simulated X-ray diffraction peaks indicate the possible existence of ort-C24 in carbon soot. These adjustable electronic topological properties may provide us with an interesting platform for studying such topological semimetals.

External Electric Field-Induced the Modulation of the Band Gap and Quantum Capacitance of F-Functionalized Two-Dimensional Sc2C.

The modulation of electronic properties and quantum capacitance of Sc2CF2 under a perpendicular external E-field was investigated using density functional calculations for the potential application of nanoelectronics and nanophotonics. Sc2CF2 has an indirect band gap of 0.959 eV without an E-field. Furthermore, it undergoes a semiconducting-metallic transition under a positive E-field and a semiconductor-insulator transition under a negative E-field. The application of the negative E-field makes Sc2CF2 have an indirect band gap. Sc-d, F-p, and C-p states are mainly responsible for the significant variation of the band gap. Sc2CF2 under an external E-field always keeps the character of a cathode material under the whole potential. Especially, Sc2CF2 under a negative external E-field is more suitable for the cathode material due to its much smaller |Qp|/|Qn| with much higher Qn. The charge analysis is further performed.

First-Principles Calculations of the Phonon, Elastic, and Thermoelectric Properties of a Ti2CO2 Monolayer.

The phonon, elastic, and thermoelectric properties of Ti2CO2 are investigated by first-principles calculations. The dynamic and mechanical stabilities of Ti2CO2 are confirmed. The Ti2CO2 monolayer exhibits strong acoustic-optical coupling with the lowest optical frequency of 122.83 cm-1. The TA mode originates from the contribution of Ti(XY) vibrations and has the largest gruneisen parameter at the Γ point; the LA mode has the main contribution of O(XY) and Ti(XY) vibrations and has the lowest gruneisen parameter at the M point. The analysis of the phonon spectrum indicates that the vibration contributions from C, O, and Ti atoms are mainly located in the low-, middle-, and high-energy regions, respectively. The Seebeck coefficient and electronic conductivity increase with increasing carrier concentration under room temperature. The analysis of mechanical properties shows that Ti2CO2 possesses a larger Young's modulus and bending modulus, which has a better ability to resist deformation. Thermal properties are further investigated.

First-principles study of high-pressure behavior of solid beta-HMX.

A first-principles plane-wave method with an ultrasoft pseudopotential scheme in the framework of the generalized gradient approximation (GGA) was used to calculate the lattice parameters, bulk modulus and its pressure derivative, energy band structures, density of states, phonon density of states, thermodynamic properties, and absorption spectra of solid beta-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (beta-HMX). The current study is focused on the thermodynamics and electronic properties that were not reported previously. The bulk modulus and its pressure derivative are also consistent with experimental data and other theoretical results. From the results for the band gaps and density of states, it was found that beta-HMX has the tendency to become a semiconductor with increasing pressure. As the temperature increases, the heat capacity, enthalpy, product of temperature and entropy, and Debye temperature all increase, whereas the free energy decreases. The optical absorption coefficients shift to higher frequencies/energies with increasing pressure. The present study leads to a better understanding of how energetic materials respond to compression.

Strain-Induced Band Modulation, Work Function, and QTAIM Analysis of Surface O-Functionalized Ti2C MXene.

Functionalized MXenes have wide applications in the fields of gas sensors, thermoelectric materials, and hydrogen storage. Strain-induced band engineering and the work function (WF) of Ti2CO2 MXene are investigated theoretically. The calculations reveal that Ti2CO2 MXenes are stable because of the negative E coh, and all the strains considered are within the elastic limit. For Ti2CO2 MXene, strain-induced blue shift of the Ti d state results in the transformation from a semiconductor to a metal. At about 4%, Ti2CO2 MXene transforms from an indirect band gap to a direct band gap. The decreased WF induced by the strain improves the power efficiency of Ti2CO2 MXene.

Pressure-Induced Modulation of Electronic and Optical Properties of Surface O-Functionalized Ti2C MXene.

Functionalized MXenes have gained increasing interest in the fields of thermoelectric materials, hydrogen storage, and so forth. In this work, pressure-induced band modulation and optical properties of the Ti2CO2 monolayer are investigated by using density functional theory with the hybrid (HSE06) functional. The calculation reveals that Ti2CO2 MXenes under pressure are stable because of the positive E coh. Ti2CO2 undergoes a semiconductor-to-metal phase transition at about 7 GPa. The metallization of Ti2CO2 mainly results from the Ti-d state. Research indicates that there exist strong interactions between Ti-d and C-p, and Ti-d and O-p states, which are further confirmed by the charge analysis. In addition, the absorption is enhanced in the visible region with increasing pressure. We also observed some new absorption peaks in the visible region.

Theoretical investigation on vibrational spectra, first order hyperpolarizability and NBO analysis of 4-Phenylpyridinium hydrogen squarate.

The vibrational frequencies of 4-Phenylpyridinium hydrogen squarate (4PHS) in the ground state have been investigated by using B3LYP/6-311++G(d,p) level. The analysis of molecular structure, natural bond orbitals and frontier molecular orbitals was also performed. The IR spectra were obtained and interpreted by means of potential energies distributions (PEDs) using MOLVIB program. NBO analysis proved the presence of C-H⋯O and N-H⋯O hydrogen bonding interactions, which is consistent with the analysis of molecular structure. The dipole moments and first-order hyperpolarizability (ßtot) are calculated and are 5.856 D and 4.72×10(-30) esu, respectively. The high ßtot value and the low HOMO-LUMO energy gap (4.062eV) are responsible for the optical and electron-transfer properties of 4PHS molecule. The photoresponse-related results indicate that 4PHS molecule is an excellent organic candidate of photon-responsive materials.