Saswata Bhattacharya

Band gap engineering by functionalization of BN sheet

From first principles calculations, we investigate the stability and physical properties of single layer h-BN sheet chemically functionalized by various groups viz. H, F, OH, CH3, CHO, CN, NH2 etc. We find that full functionalization of h-BN sheet with these groups lead to decrease in its electronic band gap, albeit to different magnitudes varying from 0.3 eV to 3.1 eV, depending upon the dopant group. Functionalization by CHO group, in particular, leads to a sharp decrease in the electronic band gap of the pristine BN sheet to ~ 0.3 eV, which is congenial for its usage in transistor based devices. The phonon calculations on these sheets show that frequencies corresponding to all their vibrational modes are real (positive), thereby suggesting their inherent stability. The chemisorption energies of these groups to the B and N atoms of the sheet are found to lie in the range of 1.5 -6 eV.

Stability and metastability of clusters in a reactive atmosphere: Theoretical evidence for unexpected stoichiometries of MgMOx

By applying a genetic algorithm and ab initio atomistic thermodynamics, we identify the stable and metastable compositions and structures of MgMOx clusters at realistic temperatures and oxygen pressures. We find that small clusters (M≲5) are in thermodynamic equilibrium when x>M. The nonstoichiometric clusters exhibit peculiar magnetic behavior, suggesting the possibility of tuning magnetic properties by changing environmental pressure and temperature conditions. Furthermore, we show that density-functional theory with a hybrid exchange-correlation functional is needed for predicting accurate phase diagrams of metal-oxide clusters. Neither a (sophisticated) force field nor density-functional theory with (semi)local exchange-correlation functionals is sufficient for even a qualitative prediction.

Strain-induced band-gap deformation of H/F passivated graphene andh-BN sheet

Strain induced band gap deformations of hydrogenated/fluorinated graphene and hexagonal BN sheet have been investigated using first principles density functional calculations. Within harmonic approximation, the deformation is found to be higher for hydrogenated systems than for the fluorinated systems. Interestingly, our calculated band gap deformation for hydrogenated/fluorinated graphene and BN sheets are positive, while those for pristine graphene and BN sheet are found to be negative. This is due to the strong overlap between nearest neighbor {\pi} orbitals in the pristine sheets, that is absent in the passivated systems. We also estimate the intrinsic strength of these materials under harmonic uniaxial strain, and find that the in-plane stiffness of fluorinated and hydrogenated graphene are close, but larger in magnitude as compared to those of fluorinated and hydrogenated BN sheet.

Exploring semiconductor substrates for silicene epitaxy

We have carried out first-principles density functional theory based calculations on electronic properties of silicene monolayer on various (111) semi-conducting surfaces. We find that the relative stability and other properties of the silicene overlayer depend sensitively on whether the interacting top layer of the substrate is metal or non-metal terminated. The nature of silicene-monolayer on the metal terminated surface can be metallic or even magnetic, depending upon the choice of the substrate. The silicene overlayer undergoes n-type doping on metal terminated surface while it undergoes p-type doping on nonmetal terminated surfaces of the semiconductor substrates.

Formation of Water Chains on CaO(001): What Drives the 1D Growth?

Formation of partly dissociated water chains is observed on CaO(001) films upon water exposure at 300 K. While morphology and orientation of the 1D assemblies are revealed from scanning tunneling microscopy, their atomic structure is identified with infrared absorption spectroscopy combined with density functional theory calculations. The latter exploit an ab initio genetic algorithm linked to atomistic thermodynamics to determine low-energy H2O configurations on the oxide surface. The development of 1D structures on the C4v symmetric CaO(001) is triggered by symmetry-broken water tetramers and a favorable balance between adsorbate-adsorbate versus adsorbate-surface interactions at the constraint of the CaO lattice parameter.

A fast and effective approach for reversible wetting-dewetting transitions on ZnO nanowires

Here, we demonstrate a facile approach for the preparation of ZnO nanowires (NWs) with tunable surface wettability that can be manipulated reversibly in a controlled manner from a superhydrophilic state to a superhydrophobic state. The as-synthesized ZnO NWs obtained by a chemical vapor deposition method are superhydrophilic with a contact angle (CA) value of ~0°. After H2 gas annealing at 300 °C for 90 minutes, ZnO NWs display superhydrophobic behavior with a roll-off angle less than 5°. However, O2 gas annealing converts these superhydrophobic ZnO NWs into a superhydrophilic state. For switching from superhydrophobic to superhydrophilic state and vice versa in cyclic manner, H2 and O2 gas annealing treatment was used, respectively. A model based on density functional theory indicates that the oxygen-related defects are responsible for CA switching. The water resistant properties of the ZnO NWs coating is found to be durable and can be applied to a variety of substrates including glass, metals, semiconductors, paper and even flexible polymers.

Computational design of nanoclusters by property-based genetic algorithms: Tuning the electronic properties of (TiO2 )n clusters

In order to design clusters with desired properties, we have implemented a suite of genetic algorithms tailored to optimize for low total energy, high vertical electron affinity (VEA), and low vertical ionization potential (VIP). Applied to

Efficient ab initio schemes for finding thermodynamically stable and metastable atomic structures: benchmark of cascade genetic algorithms

{(\mathrm{Ti}{\mathrm{O}}_{2})}_{n}

Unraveling The Origin of Enhanced Field Emission from Irradiated FeCo-SiO2 Nanocomposites: A Combined Experimental and First-Principles Based Study

clusters, the property-based optimization reveals the underlying structure-property relations and the structural features that may serve as active sites for catalysis. High VEA and low VIP are correlated with the presence of several dangling-O atoms and their proximity, respectively. We show that the electronic properties of

Theoretical evidence for unexpected O-rich phases at corners of MgO surfaces

{(\mathrm{Ti}{\mathrm{O}}_{2})}_{n}