Rajeev Ahuja

Experimental evidence for sub-3-fs charge transfer from an aromatic adsorbate to a semiconductor

The ultrafast timescale of electron transfer processes is crucial to their role in many biological systems and technological devices. In dye-sensitized solar cells, the electron transfer from photo-excited dye molecules to nanostructured semiconductor substrates needs to be sufficiently fast to compete effectively against loss processes and thus achieve high solar energy conversion efficiencies. Time-resolved laser techniques indicate an upper limit of 20 to 100 femtoseconds for the time needed to inject an electron from a dye into a semiconductor, which corresponds to the timescale on which competing processes such as charge redistribution and intramolecular thermalization of excited states occur. Here we use resonant photoemission spectroscopy, which has previously been used to monitor electron transfer in simple systems with an order-of-magnitude improvement in time resolution, to show that electron transfer from an aromatic adsorbate to a TiO2 semiconductor surface can occur in less than 3 fs. These results directly confirm that electronic coupling of the aromatic molecule to its substrate is sufficiently strong to suppress competing processes.

Physisorption of nucleobases on graphene: Density-functional calculations

We report the results of our first-principles investigation on the interaction of the nucleobases adenine (A), cytosine (C), guanine (G), thymine (T), and uracil (U) with graphene, carried out with ...

Materials science - The hardest known oxide

A material as hard as diamond or cubic boron nitride has yet to be identified, but here we report the discovery of a cotunnite-structured titanium oxide which represents the hardest oxide known. This is a new polymorph of titanium dioxide, where titanium is nine-coordinated to oxygen in the cotunnite (PbCl2) structure. The phase is synthesized at pressures above 60 gigapascals (GPa) and temperatures above 1,000 K and is one of the least compressible and hardest polycrystalline materials to be described.

Phonon related properties of transition metals, their carbides, and nitrides: A first-principles study

Lattice dynamics of body-centered cubic (bcc) Vb-VIb group transition metals (TM), and B1-type monocarbides and mononitrides of IIIb-VIb transition metals are studied by means of first-principles density functional perturbation theory, ultra soft pseudopotentials, and generalized gradient approximation to the exchange-correlation functional. Ground state parameters of transition metals and their compounds are correctly reproduced with the generated ultrasoft pseudopotentials. The calculated phonon spectra of the bcc metals are in excellent agreement with results of inelastic neutron scattering experiments. We show that the superconductivity of transition metal carbides (TMC) and transition metal nitrides (TMN) is related to peculiarities of the phonon spectra, and the anomalies of the spectra are connected to the number of valence electrons in crystals. The calculated electron-phonon interaction constants for TM, TMC, and TMN are in excellent agreement with experimentally determined values. Phonon spectra...

CARBON NANOMATERIALS AS CATALYSTS FOR HYDROGEN UPTAKE AND RELEASE IN NAALH4

A synergistic approach involving experiment and first-principles theory not only shows that carbon nanostructures can be used as catalysts for hydrogen uptake and release in complex metal hydrides such as sodium alanate, NaAlH(4), but also provides an unambiguous understanding of how the catalysts work. Here we show that the stability of NaAlH(4) originates with the charge transfer from Na to the AlH(4) moiety, resulting in an ionic bond between Na(+) and AlH(4)(-) and a covalent bond between Al and H. Interaction of NaAlH(4) with an electronegative substrate such as carbon fullerene or nanotube affects the ability of Na to donate its charge to AlH(4), consequently weakening the Al-H bond and causing hydrogen to desorb at lower temperatures as well as facilitating the absorption of H(2) to reverse the dehydrogenation reaction. In addition, based on our experimental observations and theoretical calculations it appears the curvature of the carbon nanostructure plays a role in the catalytic process. Ab initio molecular dynamics simulation further reveals the time evolution of the charge transfer process.

Li-decorated metal-organic framework 5 : A route to achieving a suitable hydrogen storage medium

A significant improvement in molecular hydrogen uptake properties is revealed by our ab initio calculations for Li-decorated metal–organic framework 5. We have found that two Li atoms are strongly adsorbed on the surfaces of the six-carbon rings, one on each side, carrying a charge of +0.9e per Li atom. Each Li can cluster three H2 molecules around itself with a binding energy of 12 kJ (mol H2)−1. Furthermore, we show from ab initio molecular dynamics simulations with a hydrogen loading of 18 H2 per formula unit that a hydrogen uptake of 2.9 wt % at 200 K and 2.0 wt % at 300 K is achievable. To our knowledge, this is the highest hydrogen storage capacity reported for metal–organic framework 5 under such thermodynamic conditions.

Stability of the body-centred-cubic phase of iron in the Earth's inner core

Iron is thought to be the main constituent of the Earths core, and considerable efforts have therefore been made to understand its properties at high pressure and temperature. While these efforts have expanded our knowledge of the iron phase diagram, there remain some significant inconsistencies, the most notable being the difference between the ‘low’ and ‘high’ melting curves. Here we report the results of molecular dynamics simulations of iron based on embedded atom models fitted to the results of two implementations of density functional theory. We tested two model approximations and found that both point to the stability of the body-centred-cubic (b.c.c.) iron phase at high temperature and pressure. Our calculated melting curve is in agreement with the ‘high’ melting curve, but our calculated phase boundary between the hexagonal close packed (h.c.p.) and b.c.c. iron phases is in good agreement with the ‘low’ melting curve. We suggest that the h.c.p.–b.c.c. transition was previously misinterpreted as a melting transition, similar to the case of xenon, and that the b.c.c. phase of iron is the stable phase in the Earths inner core.

Structure and bulk modulus of M2AlC (M=Ti, V, and Cr)

We have performed theoretical studies of the bulk modulus of M2AlC, where M=Ti, V, Cr by means of ab initio total energy calculations using the projector augmented wave methods. Our estimated equilibrium volume and the lattice parameters (c/a) agree well (within ±2% and ±0.06%, respectively) with experimental data. The bulk modulus of M2AlC increases as Ti is substituted with V and Cr by 19% and 36%, respectively. This can be understood since the substitution of Ti by V and Cr is associated with an extensive increase in the M–Al and M–C bond energy.

Magnetism and band gap narrowing in Cu-doped ZnO

First-principles calculations based on density functional theory are performed to study the magnetic, electronic, and optical properties of ZnO doped with 6.25%, 12.5%, and 18.75% of Cu. The Cu dopants are found spin polarized, and a net magnetic moment of 0.57μB is found for Cu at a composition of 6.25%. The calculations confirm an appreciable band gap reduction in ZnO in agreement with recent experimental results. The analysis of the partial density of states reveals that ferromagnetism and narrowing of ZnO band gap are due principally to the strong p-d mixing of O and Cu.

Experimental and theoretical identification of a new high-pressure phase of silica

Following the discovery of stishovite (the highest-pressure polymorph of silica known from natural samples), many attempts have been made to investigate the possible existence of denser phases of silica at higher pressures. Based on the crystal structures observed in chemical analogues of silica, high-pressure experiments on silica and theoretical studies, several possible post-stishovite phases have been suggested. But the likely stable phase of silica at pressures and temperatures representative of Earths lower mantle remains uncertain. Here we report the results of an X-ray diffraction study of silica that has been heated to temperatures above ∼2,000 K and maintained at pressures between 68 and 85 GPa. We observe the occurrence of a new high-pressure phase which we identify with the aid of first-principles total-energy calculations. The structure of this phase (space group Pnc2) is intermediate between the α-PbO2 and ZrO2 structures, and is denser than other known silica phases.