A systematic DFT study of structure and electronic properties of titanium dioxide.

DFT functionals are of paramount importance for an accurate electronic and structural description of transition metal systems. In this work, a systematic analysis using some well-known and commonly used DFT functionals is performed. A comparison of the structural and energetic parameters calculated with the available experimental data is made in order to find the adequate functional for an accurate description of the TiO bulk and surface of both anatase and rutile structures.

Role of magnetization on catalytic pathways of non-oxidative methane activation on neutral iron carbide clusters.

Methane has emerged as a promising fuel due to its abundance and clean combustion properties. It is also a raw material for various value-added chemicals. However, the conversion of methane to other chemicals such as olefins, aromatics, and hydrocarbons is a difficult task.

Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A.

We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes.

Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study.

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales.

Elucidating the enhancement in optical properties of low band gap polymers by tuning the structure of alkyl side chains.

We carry out a computational study of optical properties of two novel 5,6-difluorobenzo[c][1,2,5]-thiadiazole-based polymers, PFBT-T20TT and PFBT-T12TT, to elucidate the surprisingly superior performance of polymer solar cells based on the former, when it differs from the latter only in the alkyl side chains. Density Functional Theory (DFT) based geometry optimization at the B3LYP/6-31G(d) level reveals differences in internal coordinates, which are important in tuning the electronic and optical properties. We further calculate the electronic structure at room temperature by employing molecular dynamics (MD) simulations in combination with DFT techniques.

Sub-Ohmic spin-boson model with off-diagonal coupling: ground state properties.

We have carried out analytical and numerical studies of the spin-boson model in the sub-ohmic regime with the influence of both the diagonal and the off-diagonal coupling accounted for, via the Davydov D1 variational ansatz. While a second-order phase transition is known to be exhibited by this model in the presence of diagonal coupling only, we demonstrate the emergence of a discontinuous first order phase transition upon incorporation of the off-diagonal coupling. A plot of the ground state energy versus magnetization highlights the discontinuous nature of the transition between the isotropic (zero magnetization) state and nematic (finite magnetization) phases.

Disorder influenced absorption line shapes of a chromophore coupled to two-level systems.

We have carried out a theoretical and numerical study of disorder-induced changes in the absorption line shape of a chromophore embedded in a host matrix. The stochastic sudden jump model is employed wherein the host matrix molecules are treated as noninteracting two-level systems (TLSs) occupying points on a three-dimensional lattice with randomly oriented dipole moments. By systematically controlling the degree of positional disorder (α) attributed to them, a perfectly crystalline (α = 0) or a glassy environment (α = 1) or a combination of the two is obtained.

Investigation of the effects of commensurability on friction between concentric carbon nanotubes.

That a commensurate contact usually leads to greater friction than an incommensurate one is a commonly held view in nanotribology. However, this perception seems paradoxical as commensurability is found to have negligible effect on the energy dissipation in double-walled carbon nanotube (DWNT) based oscillators. Using molecular dynamics simulations, we investigate such a paradox from the viewpoint of the atomic origin of friction.

Thermal-gradient-induced interaction energy ramp and actuation of relative axial motion in short-sleeved double-walled carbon nanotubes.

We investigate the phenomenon of actuation of relative linear motion in double-walled carbon nanotubes (DWNTs) resulting from a temperature gradient. Molecular dynamics simulations of DWNTs with short outer tube reveal that the outer tube is driven towards the cold end of the long inner tube. It is also found that the terminal velocity of the sleeve roughly depends linearly on the applied thermal gradient.

Tight binding description on the band gap opening of pyrene-dispersed graphene.

Opening up a band gap in graphene holds a crucial significance in the realization of graphene-based electronics. Doping with organic molecules to alter the electronic properties of graphene is perceived as an effective band gap engineering approach. Using the tight binding model, we examined the band gap opening of monolayer graphene due to the adsorption of pyrene molecules on both of its sides.

Sustained smooth dynamics in short-sleeved nanobearings based on double-walled carbon nanotubes.

We carry out a molecular dynamics study of nanobearings based on double-walled carbon nanotubes with a short rotating outer tube. A (4, 4)/(9, 9) bearing configuration shows peculiar stabilization of rotational motion at certain values of angular velocities. The observed trend is found at those values of initial angular velocities (in the current context, 0.

Schematic construction of flanged nanobearings from double-walled carbon nanotubes.

The performance of nanobearings constructed from double walled carbon nanotubes is considered to be crucially dependent on the initial rotational speed. Wearless rotation ceases for a nanobearing operating beyond a certain angular velocity. We propose a new design of nanobearings by manipulation of double walled carbon nanotubes leading to a flanged structure which possesses a built-in hindrance to the intertube oscillation without obstructing rotational motion.