Optical excitations in organic molecules, clusters and defects studied by first-principles Green's function methods

Spectroscopic and optical properties of nanosystems and point defects are discussed within the framework of Green's function methods. We use an approach based on evaluating the self-energy in the so-called GW approximation and solving the Bethe-Salpeter equation in the space of single-particle transitions. Plasmon-pole models or numerical energy integration, which have been used in most of the previous GW calculations, are not used. Fourier transforms of the dielectric function are also avoided. This approach is applied to benzene, naphthalene, passivated silicon clusters (containing more than one hundred atoms), and the F center in LiCl. In the latter, excitonic effects and the $1s \to 2p$ defect line are identified in the energy-resolved dielectric function. We also compare optical spectra obtained by solving the Bethe-Salpeter equation and by using time-dependent density functional theory in the local, adiabatic approximation. From this comparison, we conclude that both methods give similar predictions for optical excitations in benzene and naphthalene, but they differ in the spectra of small silicon clusters. As cluster size increases, both methods predict very low cross section for photoabsorption in the optical and near ultra-violet ranges. For the larger clusters, the computed cross section shows a slow increase as function of photon frequency. Ionization potentials and electron affinities of molecules and clusters are also calculated.Comment: 9 figures, 5 tables, to appear in Phys. Rev. B, 200

Monoclonal antibody detects Ag polymorphism of apolipoprotein B

AbstractA monoclonal antibody (MB-19) was used to investigate the polymorphism of apolipoprotein B in a large family and in unrelated subjects. Apolipoprotein B was shown to exhibit high-, intermediate- or low-affinitybinding to this antibody. Thus, MB-19 bound strongly to the Ag(c) epitope, an Ag antigenic domain previously characterized by human antisera, while it bound only weakly to the allelic epitope Ag(g). It proved therefore useful for the detection of the two corresponding allelic apoB species designated apoBc (high-affinity binding) and apoBg (low-affinity binding), and for confirming their co-dominant transmission. Intermediate binding resulted from the presence of a mixture of both apoB populations in heterozygous subjects

Dialkylimidazolium chloroaluminates: Ab initio calculations, Raman and neutron scattering measurements

The Raman and neutron scattering spectra of 46 mol% AlCl[sub 3] -54 mol% 1-ethyl-3-methyl imidazolium chloride (EMIC) and 67 mol% AlCl[sub 3] - 33 mol% EMIC melts are presented. Ab initio molecular orbital calculations have been carried out on structures of chloroaluminate anion and EMI cation and the interaction between anion and cation

Dialkylimidazolium Chloroaluminates: Ab Initio Calculations, Raman and Neutron Scattering Measurements

The Raman and neutron scattering spectra of 46 mol% AlCl{sub 3} -54 mol% 1-ethyl-3-methyl imidazolium chloride (EMIC) and 67 mol% AlCl{sub 3} - 33 mol% EMIC melts are presented. Ab initio molecular orbital calculations have been carried out on structures of chloroaluminate anion and EMI cation and the interaction between anion and cation

Theoretical study of O adlayers on Ru(0001)

Recent experiments performed at high pressures indicate that ruthenium can support unusually high concentrations of oxygen at the surface. To investigate the structure and stability of high coverage oxygen structures, we performed density functional theory calculations, within the generalized gradient approximation, for O adlayers on Ru(0001) from low coverage up to a full monolayer. We achieve quantitative agreement with previous low energy electron diffraction intensity analyses for the (2x2) and (2x1) phases and predict that an O adlayer with a (1x1) periodicity and coverage of 1 monolayer can form on Ru(0001), where the O adatoms occupy hcp-hollow sites.Comment: RevTeX, 6 pages, 4 figure

Direct Visualization of 3-Dimensional Force and Energy Map of a Single Molecular Switch

Mechanical properties of molecules adsorbed on materials surfaces are increasingly vital for the applications of molecular thin films. Here, we conduct a fundamental research to induce conformational change mechanically on a single molecule and quantify the driving force needed for such molecular shape switch via a low temperature (~ 5K) Scanning Tunneling Microscope (STM) and Qplus Atomic Force Microscope (Q+AFM). Our measurement maps a three-dimensional landscape for mechanical potential and force at single molecule level with high spatial resolution in all three dimensions of a few angstrom (10-10 m). Molecule TBrPP-Co (a cobalt porphyrin) deposited on an atomically clean gold substrate typically has two of its pentagon rings tilted upward and the other two downward. An atomically sharp tip of the STM/Q+AFM, which vibrates with a high frequency (~ 30kHz), is employed to scan the molecule at different heights with 0.1Å increment and meanwhile record tip-molecule interaction strength in the form of tip frequency change. When tip approaches to the threshold distance to the molecule, mechanical force become large enough and cause pentagon rings flip their direction. Due to the sensitive nature of tip-molecule interaction, the rings flipping can be directly visualized by STM, as rings tilting upward exhibit two bright protrusions in contrast to rings downward in image. By processing frequency change, we obtain a three-dimensional mechanical potential and force map for a single molecule with the resolution of angstrom level in all three dimensions. Our preliminary results indicate that an energy barrier of ~400meV needs to be overcome for rings flipping of TBrPP-Co.https://digitalcommons.odu.edu/gradposters2021_sciences/1015/thumbnail.jp

Electron affinities of the first- and second- row atoms: benchmark ab initio and density functional calculations

A benchmark ab initio and density functional (DFT) study has been carried out on the electron affinities of the first- and second-row atoms. The ab initio study involves basis sets of $spdfgh$ and $spdfghi$ quality, extrapolations to the 1-particle basis set limit, and a combination of the CCSD(T), CCSDT, and full CI electron correlation methods. Scalar relativistic and spin-orbit coupling effects were taken into account. On average, the best ab initio results agree to better than 0.001 eV with the most recent experimental results. Correcting for imperfections in the CCSD(T) method improves the mean absolute error by an order of magnitude, while for accurate results on the second-row atoms inclusion of relativistic corrections is essential. The latter are significantly overestimated at the SCF level; for accurate spin-orbit splitting constants of second-row atoms inclusion of (2s,2p) correlation is essential. In the DFT calculations it is found that results for the 1st-row atoms are very sensitive to the exchange functional, while those for second-row atoms are rather more sensitive to the correlation functional. While the LYP correlation functional works best for first-row atoms, its PW91 counterpart appears to be preferable for second-row atoms. Among ``pure DFT'' (nonhybrid) functionals, G96PW91 (Gill 1996 exchange combined with Perdew-Wang 1991 correlation) puts in the best overall performance. The best results overall are obtained with the 1-parameter hybrid modified Perdew-Wang (mPW1) exchange functionals of Adamo and Barone [J. Chem. Phys. {\bf 108}, 664 (1998)], with mPW1LYP yielding the best results for first-row, and mPW1PW91 for second-row atoms. Indications exist that a hybrid of the type $a$ mPW1LYP + $(1-a)$ mPW1PW91 yields better results than either of the constituent functionals.Comment: Phys. Rev. A, in press (revised version, review of issues concerning DFT and electron affinities added