Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Vita. Includes source code for computer programs in Fortran. Includes (as Part IV): Some molecular collision integrals for point attraction and repulsion potentials / By M.A. Eliason, D.E. Stogryn, and J.O. Hirschfelder. Reprinted from Proceedings of the National Academy of Sciences, vol. 42, no. 8 (Aug. 1956), p. [546]-559 -- (as Part V): The estimation of the transport properties for electronically excited atoms and molecules / By Joseph O. Hirschfelder and Morton A. Eliason. Reprinted from Annals of the New York Academy of Sciences, vol. 67, article 9 (24 May 1957), p. 451-461. Includes bibliographical references.

In 1915, Debye derived his well-known equation for the X-ray scattering from a sample of randomly orientated gas-phase molecules. He approximated the molecular scattering by adding the contributions of isolated atomic constituents. This is known as the Independent Atom Model (IAM). However, it omits the redistribution of valence electrons due to bonding, and is limited to the electronic ground state. The main proposition of this thesis is that it is worthwhile going beyond the IAM when interpreting X-ray scattering data. In part, this is motivated by the arrival of new X-ray sources called X-ray Free-Electron Lasers (XFELs). A new method called Ab Initio X-ray Diffraction (AIXRD) is introduced. It calculates the elastic X-ray molecular scattering factor directly from wave functions calculated by ab initio electronic structure theory, for instance Hartree-Fock or multiconfigurational self-consistent field. In this way, the valence electrons are correctly taken into account, and calculations based on electronically excited wave functions become possible. The wave functions must be constructed from spatial orbitals made up of Gaussian-Type Orbitals (GTOs), giving an analytical solution to the Fourier transform integrals involved, and is key to computationally efficient and accurate results. This is compared to a fast Fourier transform (FFT) method, where the electron density is computed on a 3D grid and an FFT algorithm is used to obtain the elastic X-ray molecular scattering factor. Inspired by post-crystallography experiments such as serial femtosecond crystallography and single-particle imaging at XFELs, the AIXRD method is expanded to allow accurate X-ray diffraction calculations from large molecules such as proteins. To make the underlying ab initio problem tractable, the molecule is split into fragments. In other words, the electron density is constructed by a sum of fragment contributions, as is the corresponding molecular form-factor. In this way, it is analogous to the IAM approach except that instead of isolated atoms, there are isolated fragments. A pairwise summation of fragment contributions is also used to account for fragment-fragment interactions. Various fragment definitions are compared based on their effect on the X-ray diffraction signal, and are compared to the IAM method. Finally, X-ray diffraction from molecules in specific quantum states is calculated, revealing a distinct quantum fingerprint in the X-ray diffraction, and a comparison to experiment is made. In particular, the elastic X-ray diffraction is calculated from gas-phase H2 pumped to various electronic, vibrational, and electronic states. This is expanded upon for polyatomic molecules using the harmonic approximation for the vibrational states.

One of the central concerns of computational chemistry is that of efficiency (i.e. the development of methodologies which will yield increased accuracy of prediction without requiring additional computational resources – RAM, disk space, computing time). Though the equations of quantum mechanics are known, the solutions to these equations often require a great deal of computing power. This dissertation primarily concerns the theme of improved computational efficiency (i.e. the achievement of greater accuracy with reduced computational cost). Improvements in the efficiency of computational chemistry are explored first in terms of the correlation consistent composite approach (ccCA). The ccCA methodology was modified and this enhanced ccCA methodology was tested against the diverse G3/05 set of 454 energetic properties. As computational efficiency improves, molecules of increasing size may be studied and this dissertation explored the issues (differential correlation and size extensivity effects) associated with obtaining chemically accurate (within 1 kcal mol-1) enthalpies of formation for hydrocarbon molecules of escalating size. Two applied projects are also described; these projects concerned the theoretical prediction of a novel rare gas compound, FKrOH, and the mechanism of human glutathione synthetase’s (hGS) negative cooperativity. The final work examined the prospect for the parameterization of the modified embedded atom method (MEAM) potential using first principles calculations of dimer and trimer energies of nickel and carbon systems. This method of parameterization holds promise for increasing the accuracy of simulations for bulk properties within the field of materials science.

This thesis presents Quantum Chemical calculations on the Photochemistry of Halogenated benzenes, Phytochromobilin, Ruthenium Polypyridyl complexes and 6-4 photoadducts in DNA. The work is focused on improving the understanding of a number of experimentally observed photochemical processes in these systems. New results regarding the mechanism of photodissociation of halogenated arenes, photointerconversion of phytochromobilin are presented, as well as of the photoprocesses of Ruthenium Polypyridyl complexes and new mechanistic insights in the repair of 6-4 photoadducts in DNA.

published_or_final_version / Physics / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

The field of organic-based opto-electronic devices such as organic light- emitting diodes (OLEDs) or field-effect transistors (OFETs) has grown in interest over the past two decades. Optimizing the performance of these applications requires a better understanding of the processes taking place inside the devices and especially at their interfaces. We focused in this Ph.D. work on the electronic structure of metal/organic interfaces where the charge injection mechanism occurs. The latter process can be modulated and fine tuned by the control of the work function of the metallic electrodes. Chemisorption of self-assembled monolayers (SAMs), i.e., a two-dimensional layer of polar molecules deposited onto metal surfaces proves to be an efficient way to tune the work function of electrodes in OLED and OFET devices. However, the role played by the dipole moment of the adsorbed molecules as well as the description of the electronic effects taking place at the metal/SAM interfaces are not yet well understood. Our Ph.D. work aims at rationalizing at a theoretical level (via quantum- chemical calculations) the electronic processes occurring at metal/organic interfaces. For this goal, we focused our investigations on a well-characterized system : a methanethiolated SAM on gold-(111) surface. The adsorption energy and the influence of the anchoring site on the work function shift were evaluated beforehand in order to validate our methodology. The decomposition of the interfacial dipole moment into its interfacial and molecular components was assessed in a second stage for this system following two different procedures which differ by the treatment of the molecular backbone. The incorporation of a third component, generally not treated in an explicit way, was taken into consideration to unify the description of the interface dipole. The influence of the packing density was also described. In a next step, we have extended this study by changing the SAM chemical structure and by investigating the influence of a modification of the anchoring atom, a fluorination of the methyl group and a change in the nature of the metal surface (Ag, Cu, Pt). In order to probe the influence of intermolecular interactions, we have finally considered longer alkanethiol chains having various terminal chemical functions and analyzed the influence of the structural geometry on the change in the electrostatic potential.

<p>This licentiate thesis deals with quantum chemistry methods for large systems. In particular, the thesis focuses on the efficient construction of the Coulomb and exchange matrices which are important parts of the Fock matrix in Hartree--Fock calculations.The methods described are also applicable in Kohn--Sham Density FunctionalTheory calculations, where the Coulomb and exchange matrices areparts of the Kohn--Sham matrix. Screening techniques for reducing the computational complexity of bot Coulomb and exchange computations are discussed, as well as the fast multipole method, used for efficient computation of the Coulomb matrix.</p><p>The thesis also discusses how sparsity in the matrices occurring in Hartree--Fock and Kohn--Sham Density Functional Theory calculations can be used to achieve more efficient storage of matrices as well as more efficient operations on them.</p><p>As an example of a possible type of application, the thesis includes a theoretical study of Heisenberg exchange constants, using unrestricted Kohn--Sham Density Functional Theory calculations.</p>

Ph. D. thesis, University of Hong Kong, 1979.

A binary mixture of copper (II) chloride and gold (III) chloride solutions were introduced into a FT-ICR Mass Spectrometer through electrospray ionization techniques to produce ion clusters in the gaseous state. A series of families of ion clusters were detected across a range of different concentrations and they were identified as heterometallic mono-cationic clusters with possible hydrated and ligated species present as well. Ab initio calculations on the first member of the family of hetero-metallic monocationic species detected in the mass spectra were carried out using density function theory (DFT) methods and correlation consistent (cc) basis sets. Equilibrium bond lengths and vibrational frequencies were computed and resulting values compared with published literature values. / published_or_final_version / Applied Geosciences / Master / Master of Science