DFT Modelling of Molecular Structure, Vibrational and UV-Vis Absorption Spectra of T-2 Toxin and 3-Deacetylcalonectrin

This paper discusses the applicability of optical and vibrational spectroscopies for the identification and characterization of the T-2 mycotoxin. Vibrational states and electronic structure of the T-2 toxin molecules are simulated using a density-functional quantum-mechanical approach. A numerical experiment aimed at comparing the predicted structural, vibrational and electronic properties of the T-2 toxin with analogous characteristics of the structurally similar 3-deacetylcalonectrin is performed, and the characteristic spectral features that can be used as fingerprints of the T-2 toxin are determined. It is shown that theoretical studies of the structure and spectroscopic features of trichothecene molecules facilitate the development of methods for the detection and characterization of the metabolites.

Average density of states of amorphous Hamiltonians: role of phonon mediated coupling of nano-clusters

Based on a description of an amorphous solid as a collection of coupled nanosize molecular clusters referred as basic blocks, we analyse the statistical properties of its Hamiltonian. The information is then used to derive the ensemble averaged density of the vibrational states (nonphonon) which turns out to be a Gaussian in the bulk of the spectrum and an Airy function in the low frequency regime. A comparison with experimental data for five glasses confirms validity of our theoretical predictions.

Computational study of the rovibrational spectrum of H2O-HF

In this paper we report rovibrational energy levels, transition frequencies, and intensities computed for H2O-HF using a new ab initio potential energy surface and compare with available experimental data. We use the rigid monomer approximation. A G4 symmetry-adapted Lanczos algorithm and an uncoupled product basis are employed. The rovibrational levels are computed up to J = 4. The new analytic 9-D potential is �t to 39771 counterpoise corrected CCSD(T)(F12*)/augcc- pVTZ energies and reduces to the sum of uncoupled H2O and HF potentials in the dissociation limit. On the new potential better agreement with experiment is obtained by re-assigning the R(1) transitions of two vibrational states.

Complexes formed in collisions between ultracold alkali-metal diatomic molecules and atoms

We explore the properties of 3-atom complexes of alkali-metal diatomic molecules with alkali-metal atoms, which may be formed in ultracold collisions. We estimate the densities of vibrational states at the energy of atom-diatom collisions, and find values ranging from 3.9 to 350 K$^{-1}$. However, this density does not account for electronic near-degeneracy or electron and nuclear spins. We consider the fine and hyperfine structure expected for such complexes. The Fermi contact interaction between electron and nuclear spins can cause spin exchange between atomic and molecular spins. It can drive inelastic collisions, with resonances of three distinct types, each with a characteristic width and peak height in the inelastic rate coefficient. Some of these resonances are broad enough to overlap and produce a background loss rate that is approximately proportional to the number of outgoing inelastic channels. Spin exchange can increase the density of states from which laser-induced loss may occur.

Quantum Many-Body Theory

<p>This thesis is a collection of theoretical investigations into different aspects of the broad subject of quantum many-body theory. The results are grouped into three main parts, which in turn are divided into separate self-contained sections. Some of the work is presented in the form of published papers and papers that have been submitted for publication. The first section of Part A introduces some of the concepts involved in many-body problems, by developing methods to evaluate expectation values of the form . In the rest of Part A I consider collective excitations of finite quantum systems. The calculations are confined to nuclei because the results can then be compared with the extensive investigations that have been made into collective nuclear modes. In Section AII, wavefunctions are proposed for rotational excitations of even-even nuclei. Both isoscalar and isovector nuclear modes are discussed. In particular, the l2,m> isoscalar states are investigated for both spherical and deformed even-even nuclei, and the simplest isovector wavefunction is shown to give a good description of the giant dipole resonance. In section AIII wavefunctions are proposed for compressional vibrational states of spherical nuclei. Section AIV discusses sum rules for nuclear transitions of a given electric multipolarity. It is found that the 2+ and 1- states investigated in section AII and all but one of the vibrational states discussed in AIII each exhaust a large part of the appropriate sum rule. In Part B I consider the problem of how to describe flow in quantum fluids. In particular, we want to be able to identify the physical motion represented by any given many-body wavefunction. Section BI derives a guantum mechanical velocity field for a many-body system, paying special attention to the need for a quantum continuity equation. It is found that when the wavefunction has the usual time dependence e-iwt , that the quantum velocity formula averages over all oscillatory motion, so that much of the physical nature of the flow field is lost. In section BII a particular wavefunction is proposed to represent the quantum excitation corresponding to any given potential flow field. The results obtained by considering specific examples are very encouraging. In Part C I investigate the properties of surfaces. Section CI presents a theoretical description of the tension, energy and thickness of a classical liquid-vapour interface. In section CII the classical results are extended to describe the surface of a quantum system, namely superfluid helium four. Problems occur for the quantum system if the correlations arising from the zero-point-motion of the phonon modes are included in the ground state wavefunction. Finally, in section CIII discuss generalized virial theorems that give the change in the free energy of a system undergoing an infinitesimal deformation. For example, a particular deformation gives the expression used in CII, for the surface tension of a plane quantum surface.</p>

Quantum Many-Body Theory

<p>This thesis is a collection of theoretical investigations into different aspects of the broad subject of quantum many-body theory. The results are grouped into three main parts, which in turn are divided into separate self-contained sections. Some of the work is presented in the form of published papers and papers that have been submitted for publication. The first section of Part A introduces some of the concepts involved in many-body problems, by developing methods to evaluate expectation values of the form . In the rest of Part A I consider collective excitations of finite quantum systems. The calculations are confined to nuclei because the results can then be compared with the extensive investigations that have been made into collective nuclear modes. In Section AII, wavefunctions are proposed for rotational excitations of even-even nuclei. Both isoscalar and isovector nuclear modes are discussed. In particular, the l2,m> isoscalar states are investigated for both spherical and deformed even-even nuclei, and the simplest isovector wavefunction is shown to give a good description of the giant dipole resonance. In section AIII wavefunctions are proposed for compressional vibrational states of spherical nuclei. Section AIV discusses sum rules for nuclear transitions of a given electric multipolarity. It is found that the 2+ and 1- states investigated in section AII and all but one of the vibrational states discussed in AIII each exhaust a large part of the appropriate sum rule. In Part B I consider the problem of how to describe flow in quantum fluids. In particular, we want to be able to identify the physical motion represented by any given many-body wavefunction. Section BI derives a guantum mechanical velocity field for a many-body system, paying special attention to the need for a quantum continuity equation. It is found that when the wavefunction has the usual time dependence e-iwt , that the quantum velocity formula averages over all oscillatory motion, so that much of the physical nature of the flow field is lost. In section BII a particular wavefunction is proposed to represent the quantum excitation corresponding to any given potential flow field. The results obtained by considering specific examples are very encouraging. In Part C I investigate the properties of surfaces. Section CI presents a theoretical description of the tension, energy and thickness of a classical liquid-vapour interface. In section CII the classical results are extended to describe the surface of a quantum system, namely superfluid helium four. Problems occur for the quantum system if the correlations arising from the zero-point-motion of the phonon modes are included in the ground state wavefunction. Finally, in section CIII discuss generalized virial theorems that give the change in the free energy of a system undergoing an infinitesimal deformation. For example, a particular deformation gives the expression used in CII, for the surface tension of a plane quantum surface.</p>

Normal & reversed spin mobility in a diradical by electron-vibration coupling

Abstractπ−conjugated radicals have great promise for use in organic spintronics, however, the mechanisms of spin relaxation and mobility related to radical structural flexibility remain unexplored. Here, we describe a dumbbell shape azobenzene diradical and correlate its solid-state flexibility with spin relaxation and mobility. We employ a combination of X-ray diffraction and Raman spectroscopy to determine the molecular changes with temperature. Heating leads to: i) a modulation of the spin distribution; and ii) a “normal” quinoidal → aromatic transformation at low temperatures driven by the intramolecular rotational vibrations of the azobenzene core and a “reversed” aromatic → quinoidal change at high temperatures activated by an azobenzene bicycle pedal motion amplified by anisotropic intermolecular interactions. Thermal excitation of these vibrational states modulates the diradical electronic and spin structures featuring vibronic coupling mechanisms that might be relevant for future design of high spin organic molecules with tunable magnetic properties for solid state spintronics.