Interaction of different types of nanocages (Al12N12, Al12P12, B12N12, Be12O12, Mg12O12, Si12C12 and C24) with HCN and ClCN: DFT,TD-DFT,QTAIM, and NBO calculations

In this work, the ability of different types of nanocages including Al₁₂N₁₂, Al₁₂P₁₂, Be₁₂O₁₂, B₁₂N₁₂, Si₁₂C₁₂, Mg₁₂O₁₂ and C₂₄ for the adsorption and detection of poisonous gases HCN and ClCN has been investigated, theoretically using the D3 dispersion corrected density functional theory (DFT-D3). The absorption spectra of HCN–nanocage and ClCN–nanocage complexes were calculated by the time-dependent density functional theory (TD-DFT) and compared with the calculated absorption spectrum of isolated nanocage to investigate the ability of nanocage for sensing of HCN and ClCN gases. It was found that the strongest interaction between HCN (ClCN) molecule and nanocage takes place when the molecule is adsorbed via its N atom on the surface of nanocage except for C₂₄. Also, it was shown that the Al₁₂N₁₂ is the best adsorbent for HCN and ClCN gases among the selected nanocages and Si₁₂C₁₂ is the best sensor for the detection of these gases using the electroconductivity and absorption spectroscopy techniques.     

B-, N-doped and BN codoped C60 heterofullerenes for environmental monitoring of NO and NO2: a DFT study

ABSTRACT

Using density functional theory calculations, we investigate the gas sensing performance of B-, N-doped and BN-codoped C₆₀ fullerenes towards NO and NO₂ molecules. The calculated adsorption energies and net charge-transfer values indicate that NO and NO₂ molecules have a stronger interaction with the BN-codoped fullerenes compared to the B- or N-doped ones. It is also found that the electronic properties of the BN-codoped C₆₀ exhibit a larger sensitivity towards NO and NO₂ molecules. An increase in the concentration of doped/co-doped B and N atoms tends to weaken the gas sensing ability of these systems.     

Tuning of carbon bonds by substituent effects: an ab initio study

ABSTRACT

An ab initio study, at the MP2/aug-cc-pVTZ level of theory, is performed to study σ-hole bond in binary XH₃C···CNY complexes, where X = CN, F, NO₂, CCH and Y = H, OH, NH₂, CH₃, C₂H₅, Li. This type of interaction is labelled as ‘carbon bond’, since a covalently bonded carbon atom acts as the Lewis acid in these systems. The geometrical and energetic parameters of the resulting complexes are analysed in details. The interaction energies of these complexes are between ?4.97 kJ/mol in (HCC)H₃C···CNH and ?23.07 kJ/mol in (O₂N)H₃C···CNLi. It is found that the electrostatic interaction plays a key role in the overall stabilisation of these carbon-bonded complexes. To deepen the understanding of the nature of the carbon-bonding, the molecular electrostatic potential, natural bond orbital, quantum theory of atoms in molecules and non-covalent interaction index analyses are also used. Our results indicate that the carbon bond is favoured over the C-H···C hydrogen bond in the all complexes considered and may suggest the possible important roles of the C···C interactions in the crystal growth and design.     

Preparation and characterization of polyphosphotungstate/ZrO2 nanocomposite and their sonocatalytic and photocatalytic activity under UV light illumination

Polyoxometalates (POM) supported on zirconia, H₃PW₁₂O₄₀/ZrO_2, were prepared by incorporating polyphosphotungstate into a zirconia matrix via sol-gel technique that involving the hydrolysis of zirconium (IV) n-butoxide, Zr (n-OBu)₄, as the ZrO₂ source. This insoluble and readily separable catalyst was characterized by using XRD, FT-IR, SEM, and UV diffuse reflectance spectroscopy (UV-DRS), indicating that the polyphosphotungstate was chemically attached to the zirconia supports, and primary Keggin structure remained intact. The photocatalytic and sonocatalytic activity of the supported polyphosphotungstate was tested via degradation of different dyes in aqueous solutions. The POM-ZrO₂ nanocomposite showed higher photocatalytic and sonocatalytic activity than pure polyoxometalate or pure ZrO₂.     

On the phase field modeling of crack growth and analytical treatment on the parameters

Continuum Mechanics and Thermodynamics - A thermodynamically consistent phase field model for crack propagation is analyzed. The thermodynamic driving force for the crack propagation is derived...     

Free Convection in a Square Cavity Filled with a Tridisperse Porous Medium

This work is dealing with the natural convection heat transfer in a square filled with porous medium that has been extended according to the Nield and Kuznetsov model to tridisperse porous medium. Considering impermeable walls which the horizontal ones are insulated and vertical ones are assumed to be isothermal, the governing equations are set as the three equations for momentum and three equations for energy for three phases of porosity and are numerically solved utilizing finite element method. In this study isothermal contours, streamlines and Nusselt number values are foremost criteria which are presented for three levels of porosity. The influence of various governing parameters on the heat transfer is investigated.     

Chaos analysis in attitude dynamics of a flexible satellite

Nonlinear Dynamics - In this paper, we analytically and numerically investigate chaos in attitude dynamics of a flexible satellite composed of a rigid body and two identical rigid panels attached...