The interaction of halogen molecules with SWNTs and graphene

The interaction of halogen molecules of varying electron affinity, such as iodine monochloride (ICl), bromine (Br(2)), iodine monobromide (IBr) and iodine (I(2)) with single-walled carbon nanotubes (SWNTs) and graphene has been investigated in detail. Halogen doping of the two nanocarbons has been examined using Raman spectroscopy in conjunction with electronic absorption spectroscopy and extensive theoretical calculations. The halogen molecules, being electron withdrawing in nature, induce distinct changes in the electronic states of both the SWNTs and graphene, which manifests with a change in the spectroscopic signatures. Stiffening of the Raman G-bands of the nanocarbons upon treatment with the different halogen molecules and the emergence of new bands in the electronic absorption spectra, both point to the fact that the halogen molecules are involved in molecular charge-transfer with the nanocarbons. The experimental findings have been explained through density functional theory (DFT) calculations, which suggest that the extent of charge-transfer depends on the electron affinities of the different halogens, which determines the overall spectroscopic properties. The magnitude of the molecular charge-transfer between the halogens and the nanocarbons generally varies in the order ICl > Br(2) > IBr > I(2), which is consistent with the expected order of electron affinities.

Observation of localized states in atomically thin MoS2 field effect transistor

We present electrical transport arid low frequency (1/f) noise measurements on mechanically exfoliated single, In and triLayer MoS2-based FPI devices on Si/SiO2 substrate. We find that tie electronic states hi MoS2 are localized at low temperatures (T) and conduction happens through variable range hopping (VRH). A steep increase of 1/f noise with decreasing T, typical for localized regime was observed in all of our devices. From gate voltage dependence of noise, we find that the noise power is inversely proportional to square of the number density (proportional to 1/n(2)) for a wide range of T, indicating number density fluctuations to be the dominant source of 1/f noise in these MoS2 FETs.

Quantum and variational monte-carlo interaction potentials for li2 (x1-sigma-g+)

Optimized trial functions are used in quantum Monte Carlo and variational Monte Carlo calculations of the Li₂(X ¹Σ⁺_g) potential curve. The trial functions used are a product of a Slater determinant of molecular orbitals multiplied by correlation functions of electron—nuclear and electron—electron separation. The parameters of the determinant and correlation functions are optimized simultaneously by reducing the deviations of the local energy E_L (E_L  Ψ⁻¹_THΨ_T, where Ψ_T denotes a trial function) over a fixed sample. At the equilibrium separation, the variational Monte Carlo and quantum Monte Carlo methods recover 68% and 98% of the correlation energy, respectively. At other points on the curves, these methods yield similar accuracies.

Long-lived oscillatory incoherent electron dynamics in molecules: trans-polyacetylene oligomers

We identify an intriguing feature of the electron-vibrational dynamics of molecular systems via a computational examination of trans-polyacetylene oligomers. Here, via the vibronic interactions, the decay of an electron in the conduction band resonantly excites an electron in the valence band, and vice versa, leading to oscillatory exchange of electronic population between two distinct electronic states that lives for up to tens of picoseconds. The oscillatory structure is reminiscent of beating patterns between quantum states and is strongly suggestive of the presence of long-lived molecular electronic coherence. Significantly, however, a detailed analysis of the electronic coherence properties shows that the oscillatory structure arises from a purely incoherent process. These results were obtained by propagating the coupled dynamics of electronic and vibrational degrees of freedom in a mixed quantum-classical study of the Su-Schrieffer-Heeger Hamiltonian for polyacetylene. The incoherent process is shown to occur between degenerate electronic states with distinct electronic configurations that are indirectly coupled via a third auxiliary state by vibronic interactions. A discussion of how to construct electronic superposition states in molecules that are truly robust to decoherence is also presented

Theory of ozone isotopic effects and various electron transfer reactions

Three separate topics, each stimulated by experiments, are treated theoretically in this dessertation: isotopic effects of ozone, electron transfer at interfaces, and intramolecular directional electron transfer in a supramolecular system.

The strange mass-independent isotope effect for the enrichment of ozone, which has been a puzzle in the literature for some 20 years, and the equally puzzling unconventional strong mass-dependent effect of individual reaction rate constants are studied as different aspects of a symmetry-driven behavior. A statistical (RRKM-based) theory with a hindered-rotor transition state is used. The individual rate constant ratios of recombination reactions at low pressures are calculated using the theory involving (1) small deviation from the statistical density of states for symmetric isotopomers, and (2) weak collisions for deactivation of the vibrationally excited ozone molecules. The weak collision and partitioning among exit channels play major roles in producing the large unconventional isotope effect in "unscrambled" systems. The enrichment studies reflect instead the non-statistical effect in "scrambled" systems. The theoretical results of low-pressure ozone enrichments and individual rate constant ratios obtained from these calculations are consistent with the corresponding experimental results. The isotopic exchange rate constant for the reaction ^(16)O + ^(18)O ^(18)O→+ ^(16)O ^(18)O + ^(18)O provides information on the nature of a variationally determined hindered-rotor transition state using experimental data at 130 K and 300 K. Pressure effects on the recombination rate constant, on the individual rate constant ratios and on the enrichments are also investigated. The theoretical results are consistent with the experimental data. The temperature dependence of the enrichment and rate constant ratios is also discussed, and experimental tests are suggested. The desirability of a more accurate potential energy surface for ozone in the transition state region is also noted.

Electron transfer reactions at semiconductor /liquid interfaces are studied using a tight-binding model for the semiconductors. The slab method and a z-transform method are employed in obtaining the tight-binding electronic structures of semiconductors having surfaces. The maximum electron transfer rate constants at Si/viologen^(2-/+) and InP /Me_(2)Fc^(+/O) interfaces are computed using the tight-binding type calculations for the solid and the extended-Huckel for the coupling to the redox agent at the interface. These electron transfer reactions are also studied using a free electron model for the semiconductor and the redox molecule, where Bardeen's method is adapted to calculate the coupling matrix element between the molecular and semiconductor electronic states. The calculated results for maximum rate constant of the electron transfer from the semiconductor bulk states are compared with the experimentally measured values of Lewis and coworkers, and are in reasonable agreement, without adjusting parameters. In the case of InP /liquid interface, the unusual current vs applied potential behavior is additionally interpreted, in part, by the presence of surface states.

Photoinduced electron transfer reactions in small supramolecular systems, such as 4-aminonaphthalimide compounds, are interesting in that there are, in principle, two alternative pathways (directions) for the electron transfer. The electron transfer, however, is unidirectional, as deduced from pH-dependent fluorescence quenching studies on different compounds. The role of electronic coupling matrix element and the charges in protonation are considered to explain the directionality of the electron transfer and other various results. A related mechanism is proposed to interpret the fluorescence behavior of similar molecules as fluorescent sensors of metal ions.

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot. (C) 2004 Elsevier B.V. All rights reserved.

A novel line-order of InAs quantum dots on GaAs

A novel line-order of InAs quantum dots (QDs) along the [1, 1, 0] direction on GaAs substrate has been prepared by self-organized growth. After 2.5 monolayer InAs deposition, QDs in the first layer of multi-layer samples started to gather in a line. Owing to the action of strong stress between layers, almost all the dots of the fourth layer gathered in lines. The dots lining up tightly are actually one-dimensional superlattice of QDs, of which the density of electronic states is different from that of isolated QDs or quantum wires. The photoluminescence spectra of our multi-layer QD sample exhibited a feature of very broad band so that it is suitable for the active medium of super luminescent diode. The reason of dots lining up is attributed to the hill-and-valley structure of the buffer, anisotropy and different diffusion rates in the different directions on the buffer and strong stress between QD layers. (C) 2002 Published by Elsevier Science B. V.

The second dissociation threshold bound levels of hydrogen molecule

The near-threshold highly bound states of all three stable isotopic variants of molecular hydrogen have been studied. Numerous perturbations and unexpected transitions are observed as far as 1cm(-1) just below the second dissociation threshold. This complex structure may arise from a combination of nonadiabatic coupling between B, B', C electronic states, perturbations due to. ne and hyperfine interactions, and strong shape resonances. The perturbed near-threshold states and vibrational continuum exhibit finegrained structure, differing greatly between isotopes because of varying nonadiabatic coupling.

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot. (C) 2004 Elsevier B.V. All rights reserved.

From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Charge carrier transporting, photoluminescent, and electroluminescent properties of zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex

Zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex is an excellent white-light-emitting material. Despite some studies devoted to this complex, no information on the real origin of the unusually broad electroluminescent (EL) emission is available. Therefore, we investigate photoluminescent and EL properties of the zinc complex. Orange phosphorescent emission at 580 nm was observed for the complex in thin film at 77 K, whereas only fluorescent emission was obtained at room temperature. Molecular orbitals, excitation energy, and emission energy of the complex were investigated using quantum chemical calculations. We fabricated the device with a structure of ITO/F16CuPc(5.5 nm)/Zn-complex/Al, where F16CuPc is hexadecafluoro copper phthalocyanine. The EL spectra varied strongly with the thickness of the emissive layer. We observed a significant change in the emission spectra with the viewing angles. Optical interference effects and light emission originating both from fluorescence and from phosphorescence can explain all of the observed phenomena, resulting in the broad light emission for the devices based on the Zn complex. We calculated the charge transfer integral and the reorganization energy to explain why the Zn complex is a better electron transporter than a hole transporter.

Photodissociation of 1-bromo-2-chloroethane at 266 nm

The photodissociation of CH2BrCH2Cl at 266 nm has been investigated on the universal crossed molecular beam machine. The primary dissociation step leads exclusively to the formation of CH2CH2Cl radicals and Br atoms in the electronic ground state as well as in the spin-orbit excited state, with a branching ratio 2 +/- 1:8 +/- 1. Photofragment total c.m. translational energy distribution P(E-t) has been obtained and about 64% of the available energy is partitioned into translational energy for Br channel and about 28.5% of the available energy is partitioned into translational energy for Br* channel. The anisotropy parameters are determined to be beta(Br*) = 0.8 +/- 0.2 and beta(Br) = -0.6 +/- 0.2, respectively. Some CH2CH2Cl radicals with large internal excitation (corresponding to formation of ground state Br channel) may undergo secondary dissociation to form CH2CH2 +/- Cl. The experimental results are discussed in terms of a model that involves the initial excitation of two repulsive electronic states: one from an parallel transition to the (3)Q(0) state, and the other from a perpendicular transition to the (3)Q(1), (1)Q states. (C) 1999 Elsevier Science B.V. All rights reserved.

Electronic spectroscopy of thiones

The phosphorescence excitation spectra of two thiones, 4-H-1-xanthione (XT) and 4-H-1-pyrane-4-thione (PT), cooled in a supersonic jet were investigated. The vibronic lineshape of the T1z origin of PT measured by cavity ring-down spectroscopy is considered and the excited state rotational constants are calculated. For XT the 3A2(nπ* ) → X1A1 phosphorescence excitation spectrum was investigated in the region 14900-17600 cm-1. The structure observed is shown to be due to the T1← S0 absorption and an assignment in terms of the vibronic structure of the band is proposed. A previous assignment of the S1 ← S0 origin is considered and the transition involved is shown to be most probably due to the absorption of a vibronic tiplet state T1z,v7. An alternative but tentative assignment of the S1,0 ←S0,0 transition is suggested. In the case of PT the phosphorescence excitation spectrum was investigated in the region of the 1A2(ππ*) ← X1A1 absorption band between 27300 and 28800 cm-1. The spectrum exhibits complex features which are typical for the strong vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ*2), whose origin was estimated to be ~ 825 - 1025 cm-1 below the origin of 1A2(ππ*)0. Consequences of the vibronic coupling on the decay dynamics of 1A2(ππ*) as well as tentative assignments of vibronic transitions 1A2(ππ*)v ← X1A1 are also discussed. In the T1z ← S0 cavity ring-down absorption spectrum of PT, the vibronic lineshape of the T1z origin is analysed. As the T1z line is separated from the T1x,1y lines by a large zero-field splitting it is possible to use an Asyrot-like program to calculate the vibrational-rotational parameters determining the lineshape. It is shown that PT is non-planar in the first excited triplet state and the lineshape is composed of a mixture of A-type and C-type bandshapes. The non-planarity of PT is discussed.

First principles simulation of amorphous silicon bulk, interfaces, and nanowires for photovoltaics

Amorphous silicon has become the material of choice for many technologies, with major applications in large area electronics: displays, image sensing and thin film photovoltaic cells. This technology development has occurred because amorphous silicon is a thin film semiconductor that can be deposited on large, low cost substrates using low temperature. In this thesis, classical molecular dynamics and first principles DFT calculations have been performed to generate structural models of amorphous and hydrogenated amorphous silicon and interfaces of amorphous and crystalline silicon, with the ultimate aim of understanding the photovoltaic properties of core-shell crystalline amorphous Si nanowire structures. We have shown, unexpectedly, from the simulations, that our understanding of hydrogenated bulk a-Si needs to be revisited, with our robust finding that when fully saturated with hydrogen, bulk a-Si exhibits a constant optical energy gap, irrespective of the hydrogen concentration in the sample. Unsaturated a-Si:H, with a lower than optimum hydrogen content, shows a smaller optical gap, that increases with hydrogen content until saturation is reached. The mobility gaps obtained from an analysis of the electronic states show similar behavior. We also obtained that the optical and mobility gaps show a volcano curve as the H content is varied from 7% (undersaturation) to 18% (mild oversaturation). In the case of mild over saturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structures shows the extra H atoms in this case form a bridge between neighboring silicon atoms which increases the corresponding Si-Si distance and promotes bond length disorder in the sample. That has the potential to enhance the Staebler-Wronski effect. Planar interface models of amorphous-crystalline silicon have been generated in Si (100), (110) and (111) surfaces. The interface models are characterized by structure, RDF, electronic density of states and optical absorption spectrum. We find that the least stable (100) surface will result in the formation of the thickest amorphous silicon layer, while the most stable (110) surface forms the smallest amorphous region. We calculated for the first time band offsets of a-Si:H/c-Si heterojunctions from first principles and examined the influence of different surface orientations and amorphous layer thickness on the offsets and implications for device performance. The band offsets depend on the amorphous layer thickness and increase with thickness. By controlling the amorphous layer thickness we can potentially optimise the solar cell parameters. Finally, we have successfully generated different amorphous layer thickness of the a-Si/c-Si and a-Si:H/c-Si 5 nm nanowires from heat and quench. We perform structural analysis of the a-Si-/c-Si nanowires. The RDF, Si-Si bond length distributions, and the coordination number distributions of amorphous regions of the nanowires reproduce similar behaviour compared to bulk amorphous silicon. In the final part of this thesis we examine different surface terminating chemical groups, -H, - OH and –NH2 in (001) GeNW. Our work shows that the diameter of Ge nanowires and the nature of surface terminating groups both play a significant role in both the magnitude and the nature of the nanowire band gaps, allowing tuning of the band gap by up to 1.1 eV. We also show for the first time how the nanowire diameter and surface termination shifts the absorption edge in the Ge nanowires to longer wavelengths. Thus, the combination of nanowire diameter and surface chemistry can be effectively utilised to tune the band gaps and thus light absorption properties of small diameter Ge nanowires.

Prospects of phase resolved optical emission spectroscopy as a powerful diagnostic tool for RF-discharges

Phase resolved optical emission spectroscopy (PROES) bears considerable potential for diagnostics of RF discharges that give detailed insight of spatial and temporal variations of excitation processes. Based on phase and space resolved measurements of the population dynamics of excited states several diagnostic techniques have been developed. Results for a hydrogen capacitively coupled RF (CCRF) discharge are discussed as an example. The gas temperature, the degree of dissociation and the temporally and spatially resolved electron energy distribution function (EEDF) of energetic electrons (>12eV) are measured. Furthermore, the pulsed electron impact excitation during the field reversal phase, typical for hydrogen CCRF discharges, is exploited for measurements of atomic and molecular data like lifetimes of excited states, coefficients for radiationless collisional de-excitation (quenching coefficients), and cascading processes from higher electronic states.