Sharif Digital Repository

Transition metal lithium orthosilicates are of interest as cathode materials for lithium batteries. Density functional theory (DFT) calculations were performed to evaluate the structural and electrochemical properties of the different polymorphs of Li2MnSiO4. Our computational studies predict superior properties for the Pmn21 polymorph even after extraction of two Li per formula unit. We state that the shortcomings observed for Li2MnSiO4 as a cathode are caused by two mechanisms. Switching of the magnetic state occurs during the first cycles. The subsequent transition, under delithiated conditions, from the Pmn21 or Pmnb polymorphs to the electrochemically weakest P21/n polymorph is the... 

This paper considers scheduling tasks while minimizing the power consumption of one or more processors, each of which can go to sleep at a fixed cost α. There are two natural versions of this problem, both considered extensively in recent work: minimize the total power consumption (including computation time), or minimize the number of "gaps" in execution. For both versions in a multiprocessor system, we develop a polynomial-time algorithm based on sophisticated dynamic programming. In a generalization of the power-saving problem, where each task can execute in any of a specified set of time intervals, we develop a (1 + 23 α)-approximation, and show that dependence on α is necessary.... 

This work suggests a green method for synthesizing Au nanoparticles (AuNPs) using the aqueous extract of Salix aegyptiaca extract. The mechanism of green synthesized AuNPs was examined by molecular electrostatic potential (MEP) calculations. AuNPs were characterized with different techniques such as Ultraviolet–visible spectroscopy (UV–vis), Fourier-transform infrared spectroscopy (FT-IR) spectroscopy, X-ray diffraction (XRD), and Transmission electron microscopy (TEM). Electrochemical investigation of modified glassy carbon electrode using AuNPs (AuNPs/GCE) shows that the electronic transmission rate between the modified electrode and [Fe (CN)6]3−/4− increased. Process of oxidation, energy... 

Herein we describe the synthesis and characterization of the first platinum(IV) metal-organic cage [(Me3PtIV)8(byp)12](OTf)8 (2), in which the organometallic moieties trimethylplatinum(IV) (PtMe3) occupied the corners of a cubane structure and 4,4′-bipyridine ligands used as linkers. The first-principles density functional theory calculations showed that the highest occupied molecular orbitals were localized on the PtMe3 moieties, while the lowest unoccupied molecular orbitals were distributed on the organic linkers. © 2021 American Chemical Society  

A new di-manganese complex with "back-to-back" 1,4-bis(2,2′:6,2′′-terpyridin-4′-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were... 

A specific structure of doped graphene with substituted silicon impurity is introduced and ab initio density-functional approach is applied for the energy band structure calculation of the proposed structure. Using the band structure calculation for different silicon sites in the host graphene, the effect of silicon concentration and unit cell geometry on the bandgap of the proposed structure is also investigated. Chemically, silicon-doped graphene results in an energy gap as large as 2eV according to density-functional theory calculations. As the authors will show, in contrast to previous bandgap engineering methods, such structure has significant advantages including wide gap tuning... 

Symmetrical and unsymmetrical biscyclometalated platinum(II) complexes [Pt(ptpy)2], 1, and [Pt(ptpy)(bppy)], 2, in which ptpy = deprotonated 2-(p-tolyl)pyridine and bppy = deprotonated 2-(3-bromophenyl)pyridine, have been prepared from the reaction between tris(pentafluorophenyl)borane, B(C6F5)3 and 1 equiv of monocyclometalated complexes [PtMe(ptpy)(ptpyH)], B, and [PtMe(ptpy)(bppyH)], C, respectively. The solid-state structures of 1 and 2 have been determined by X-ray crystallography. The reaction of 1 with 1 equiv of TlPF6 or [Au(PPh3)]OTF resulted in the production of heteronuclear complexes [Pt(ptpy)2Tl]PF6, 3 and {Pt(ptpy)2[Au(PPh3)]}OTF, 4, respectively. X-ray diffraction data showed... 

This study investigates the synthesis of CuCo2O4, BiVO4, and CuCo2O4/BiVO4 nanocomposite by the solvothermal method. The Physico-chemical properties of the samples were verified through Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Transmission Electron microscope (TEM), energy-dispersive X-ray spectroscopy (EDS), Brunauer-Emmett-Teller (BET). Evaluation of catalytic efficiency of the synthesized samples were done in promoting the 4-Nitrophenol reduction to 4-Aminophenol in the existence of high amount of sodium borohydride (NaBH4) as a reducing agent, and the progress of the catalytic reaction was monitored... 

Van der Waals (vdW) heterostructures of two-dimensional monolayers are a relatively new class of materials with highly tunable band alignment, bandgap energy, and bandgap transition type. In this study, we performed density functional theory calculations to investigate how a vdW heterostructure of heptazine-based graphitic carbon nitride (hg-C3N4) and graphitic zinc oxide (g-ZnO) monolayers is formed (hg-C3N4/g-ZnO). This heterostructure is a potential solar-driven photocatalyst for the water-splitting reaction. Upon the formation of the heterostructure, a type-I indirect bandgap (Eg = 2.08 eV) is created with appropriate conduction band minimum and valence band maximum levels relative to... 

Eringen's nonlocal theory and an accurate determination of the nonlocal kernel functions for hexagonal close-packed (hcp) crystals are of interest. The kernel functions are closely related to the anisotropy as well as any crystalline symmetries. To this end, five new distinct nonlocal kernel functions which have the characteristics of discrete atomistic Green's functions in the stress space are obtained through consideration of the nonlocal dispersion relations associated with certain directions combined with ab initio Density Functional Perturbation Theory (DFPT) calculations of the pertinent phonon frequencies. This is the first work which provides the nonlocal hcp kernel functions... 

Resonance Raman spectroscopy has long been established as one of the most sensitive techniques for detection, structure characterization, and probing the excited-state dynamics of biochemical systems. However, the analysis of resonance Raman spectra is much facilitated when measurements are accompanied by Density Functional Theory (DFT) calculations that are expensive for large biomolecules. In this work, resonance Raman spectra are therefore computed with the Density Functional Tight-Binding (DFTB) method in the time-dependent excited-state gradient approximation. To test the accuracy of the tight-binding approximations, this method is first applied to typical resonance Raman benchmark... 

The optimized minimum-energy geometries of different macrocyclic amines and their protonated structures were determined by using ab initio and density functional theory (DFT) calculations. All the gas phase optimizations and energy calculations were performed at the DFT/B3LYP/6-311++G(d,p) level of theory. The HF/6-31 + G(d,p) level was used for all single point calculations in the solution phase. Geometry optimizations indicate that the most stable structures are stabilized by intramolecular hydrogen bonds. The proton affinity (PA) of macrocyclic amines is controlled by the strength of intramolecular hydrogen bonds of macrocyclic amines. These hydrogen bonds strongly influence the basicity... 

The synthesis of modified versions of deoxyribonucleic acid is an area that is receiving much attention. The replacement of the nitrogen atom on the nucleobases with boron atom has provided insight into deoxyribonucleic acid and ribonucleic acid stability, recognition, and replication at the atomic level. In the present research, we investigated a detailed density functional theory study of the structural, tautomeric, base-pairing ability, bond dissociation energy, and electronic properties of two boron analogues (i.e., boron substitutions at 4-position and 5-position of uracil) of uracil nucleobase. The effects of these modifications on theirs acid-base properties have been considered. Our... 

Mononuclear nonheme iron containing systems are versatile and vital oxidants of substrate hydroxylation reactions in many biosystems, whereby the rate constant of hydroxylation correlates with the strength of the C-H bond that is broken in the process. The thermodynamic reason behind these correlations, however, has never been established. In this work results of a series of density functional theory calculations of substrate hydroxylation by a mononuclear nonheme iron(IV)-oxo oxidant with a 2 His/ 1Asp structural motif analogous to aketoglutarate dependent dioxygenases are presented. The calculations show that these oxidants are very efficient and able to hydroxylate strong C-H bonds,... 

This study aimed to synthesize methoxy polyethylene glycol propionaldehyde (mPEG20,000-ALD) for the preparation of PEGylated nanoliposomal cisplatin. Nanocarriers such as liposomes are developed for a wide range of drug delivery systems. PEG with high molecular weight (Mw) is used to coat the liposomes. In this study, simulated Fourier transform infrared (FTIR) spectra of mPEG-ALD were obtained using density functional theory (DFT) calculations and then compared with actual FTIR spectrum of mPEG20,000-ALD (Mw = 20 kDa). We found that the intensity of C = O stretching vibration at 1,700 cm-1 related to the carbonyl functional group of mPEG20,000-ALD was very weak. The results of DFT... 

Density functional theory (DFT) calculations were performed at the B3LYP level with a 6-311++G(d,p) basis set to systematically explore the geometrical multiplicity and binding strength for complexes formed by Li+, Na+, and K+ with cytidine and 2′-deoxycytidine. All computational studies indicate that the metal ion affinity (MIA) decreases from Li+ to Na+ and K+ for cytosine nucleosides. For example, for cytidine the affinity for the above metal ions are 79.5, 55.2, and 41.8 and for 2′-deoxycytidine, 82.8, 57.4, and 42.2 kcal/mol, respectively. It is also interesting to mention that linear correlations between calculated MIA values and the atomic numbers (Z) of the above metal ions were... 

The catalytic activity of highvalent iron-oxo active species of heme enzymes is known to be dependent on the nature of the axial ligand trans to the iron-oxo group. In a similar fashion, experimental studies on iron-oxo porphyrin biomimetic systems have shown a significant axial ligand effect on ethylbenzene hydroxylation, with an axial acetonitrile ligand leading to phenyl hydroxylation products and an axial chloride anion giving predominantly benzyl hydroxylation products. To elucidate the fundamental factors that distinguish this regioselectivity reversal in iron-oxo porphyrin catalysis, we have performed a series of density functional theory calculations on the hydroxylation of...