Solvation!

This dissertation consists of two closely related parts: theory development and coding of correlation effects in a model potential for solvation, and study of solvent effects on chemical reactions and processes.;The effective fragment potential (EFP) method has been re-parameterized, using density functional theory (DFT), more specifically, the B3LYP functional. The DFT based EFP method includes short-range correlation effects; hence it is a first step in incorporating the treatment of correlation in the EFP solvation model. In addition, the gradient of the charge penetration term in the EFP model was derived and coded. The new method has been implemented in the electronic structure code GAMESS and is in use. Formulas for the dynamic dipole polarizability, C6 dispersion coefficient and dispersion energy were derived and coded as a part of a treatment of the dispersion interactions in the general solvation model, EFP2. Preliminary results are in good agreement with experimental and other theoretical data.;The DFT based EFP (EFP1/DFT) method was used in the study of microsolvation effects on the SN2 substitution reaction, between chloride and methyl bromide. Changes in the central barrier, for several lowest lying isomers of the systems with one, two, three and four waters, were studied using second order perturbation theory (MP2), DFT and mixed quantum mechanics (QM)/(EFP1/DFT) methods. EFP1IDFT is found to reproduce QM results with high accuracy, at just a fraction of the cost.;Molecular structures and potential energy surfaces for IHI- • Arn (n = 1--7) were studied using the MP2 method. Experimentally observed trends in the structural arrangement of the Ar atoms were explained through the analysis of the geometrical parameters and three-dimensional MP2 molecular electrostatic potentials

Modeling styrene-styrene interactions

This study is the first step in the systematic investigation of substituted (carboxyl) polystyrene nanoparticles. Understanding the fundamental interactions between the p-carboxyl styrene monomers, where an ethyl group is used instead of a vinyl group (referenced, for convenience, as p-carboxyl styrene ), provides the basic information needed to construct potentials for nanoparticles composed of these monomers. In this work, low-energy isomers of p-carboxyl styrene dimer were studied. The dimer structures and their relative and binding energies were determined using both Møller-Plesset second-order perturbation theory (MP2) and the general effective fragment potential (EFP2) method. Sections of the intermolecular potential energy surface (PES) of the p-carboxylated styrene dimer in its global minimum orientation were also determined. As expected, double hydrogen bonding between the two carboxylic groups provides the strongest interaction in this system, followed by isomers with a single H-bond and strong benzene ring-benzene ring (π-π) type interactions. Generally, the EFP2 method reproduces the MP2 geometries and relative energies with good accuracy, so it appears to be an efficient alternative to the correlated ab initio methods, which are too computationally demanding to be routinely used in the study of the more-complex polymeric systems of interest

Multireference Second-Order Perturbation Theory: How Size Consistent is “Almost Size Consistent”

A systematic study of the deviation from size consistency of the multireference second-order Møller-Plesset perturbation theory (MRMP2) method is presented. The size-consistency error is shown to depend on the number of monomers in a supermolecule calculation, size of basis set, number of correlated valence electrons, and size of active space. HF, F2, and N2 are used as test cases, with stretched bonds, to include simple, well-defined multireference character. This is essential in ensuring that MRMP2 is being tested as a multireference method. It is concluded that the MRMP2 and other multireference perturbation theory methods can exhibit significant size-consistency errors, and that the size of the error depends on the manner in which the perturbation theory is implemented

Formaldehyde in screen printing indoor

The presence of formaldehyde in air samples has been detected in five screen printing facilities in Novi Sad, Serbia. Air samples were sampled continuously during 4 hours, and concentration levels of formaldehyde was determined by UV-VIS spectrometry at 580 nm. The range of formaldehyde concentrations was from 0.413 to 0.836 ppm. Comparison of the detected concentration levels with the permissible exposure limit of 0.75 ppm (the OSHA standard) indicated that the formaldehyde concentration in facility 5 was 1.11 times higher than prescribed value

Potential Energy Surfaces of SimOn Cluster Formation and Isomerization

The reaction paths for formation and isomerization of a set of silica SimOn (m = 2,3, n = 1−5) nanoclusters have been investigated using second-order pertubation theory (MP2) with the 6-31G(d) basis set. The MP2/6-31G(d) calculations have predicted singlet ground states for all clusters excluding Si3O2. The total energies of the most important points on the potential energy surfaces (PES) have been determined using the completely renormalized (CR) singles and doubles coupled cluster method including perturbative triples, CR-CCSD(T) with the cc-pVTZ basis set. Although transition states have been located for many isomerization reactions, only for Si3O3 and Si3O4 have some transition states been found for the formation of a cluster from the separated reactants. In all other cases, the process of formation of SimOnclusters appears to proceed without potential energy barriers