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We show STM images that display fourfold symmetry hole states around point defects on the NiO (001) surface that are a number of times larger than the unit cell. The observation of these spatially delocalised states demonstrates that a reasonable description of bonding in NiO must go beyond a simple ionic interaction. This is achieved through the implementation of the LSDA + U model in simulating EELS spectra of the oxygen K edge. By using this method an accurate value for the electron-electron interaction parameter U of 6.2 eV can be determined, and hybridisation between O 2p and Ni 3d orbitals can be seen which points to the existence of a significant covalent contribution to bonding in NiO.

We report here on the time evolution of photoconductivity under continuous illumination in nanocrystalline TiO2 samples prepared by a sol gel method, and also on the conductivity decay once the illumination is switched off. We observe strong dependence of the photoconductivity on the illumination intensity for both processes. It is found that the conductivity decay after high-intensity illumination is slower than after low-intensity illumination, and we have attempted to explain these experimental results using a model involving hole trapping-detrapping processes.

Photoluminescence spectroscopic measurements have allowed the acquisition of high resolution spectra at low temperature for the endohedral metallofullerenes, Er2 @ C82 (isomer I) and Er2 C2 @ C82 (isomer I). The characteristic emission in the 1.5-1.6 μm region corresponds to the 4 I13 / 2 (m) → 4 I15 / 2 (n) transitions of the Er3 + ion for both molecules. The emission arising from Er2 C2 @ C82 (I) appears acuminated (narrow lines that taper to a point) when compared with that of Er2 @ C82 (I). The Er2 C2 @ C82 (I) emission linewidths are comparable to those found in crystals, making this molecule of interest for applications where accessible, well-defined quantum states are required. © 2009 Elsevier B.V. All rights reserved.

Endohedral fullerenes encapsulating single nitrogen atoms (N@C60 and N@C70) are spin active, due to the presence of unpaired nitrogen electron spins. High reactivity of nitrogen leads to a poor stability of these molecules at elevated temperatures, drastically restricting possibilities of their chemical treatment. In this study, N@C60 and N@C70 in toluene solutions were subjected to high pressure (HP) up to 0.8 GPa and annealed for 1, 2, 10 or 24 h, at either room or elevated temperatures. In each case the number of surviving molecules was evaluated based on the relative spin counts of ex situ EPR spectra obtained before and after the treatment. The enhanced thermal stability of N@C60 and N@C70 under HP conditions is attributed to inhibited formation of azabridges, which under normal pressure facilitate the escape of nitrogen from the fullerene cage. © 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.

We examine environmental effects of surrounding nuclear spins on the electron spin relaxation of the N@C60 molecule (which consists of a nitrogen atom at the centre of a fullerene cage). Using dilute solutions of N@C60 in regular and deuterated toluene, we observe and model the effect of translational diffusion of nuclear spins of the solvent molecules on the N@C60 electron spin relaxation times. We also study spin relaxation in frozen solutions of N@C60 in CS2, to which small quantities of a glassing agent, S2Cl2 are added. At low temperatures, spin relaxation is caused by spectral diffusion of surrounding nuclear 35Cl and 37Cl spins in the S2Cl2, but nevertheless, at 20 K, T2 times as long as 0.23 ms are observed., Comment: 7 pages, 6 figures

This thesis is concerned with vibrational effects in resonant charge transport through molecular junctions. The first research chapter examines the role of non-equilibrium vibrational dynamics in charge transport through a molecular double quantum dot. We demonstrate that non-equilibrium vibrational effects in such a system can result in current suppression and negative differential conductance. The second research chapter describes how vibrational dynamics can be incorporated into the theoretical description of molecular junctions based on a Pariser-Parr-Pople Hamiltonian. As a case study, we consider a prototypical spiro-conjugated molecular junction. We demonstrate that the transport properties of this system are governed by an interplay between destructive quantum interference and Jahn-Teller distortion (an effect of vibronic origin). In the next chapter, we examine the role of collective vibrational coupling in charge transport through a two-site molecular system akin to the one considered in the first research chapter. We demonstrate that such interactions can significantly enhance the efficiency of transport through such a system, and also take this opportunity to analyse various theoretical descriptions of electron-vibrational interactions commonly used in the transport setting. In the fourth research chapter, we consider a single-site molecular system coupled to a collection of thermalised vibrational modes. We formulate a relatively simple yet powerful theoretical framework describing charge transport through such a system. We recover the Marcus and Landauer-Buttiker theories of transport in the limit of high-temperature and vanishing electron-vibrational coupling, respectively. We further show how lifetime broadening can be consistently incorporated into Marcus theory, and we derive a low-temperature correction to the semi-classical Marcus hopping rates. In the last research chapter, elements of this framework are applied to experimental measurements of charge transport through zinc-porphyrin molecular junctions. This joint experimental-theoretical study provides, for the first time, a full understanding of the resonant transport regime of graphene-based molecular junctions.