Beyond Transition State Theory: Accurate Description of Nuclear Quantum Effects on the Rate and Equilibrium Constants of Chemical Reactions Using Feynman Path Integrals
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This thesis deals with a laboratory study of heterogeneous reactions involving bromine and chlorine containing reservoir species on alkali salt substrates which are relevant to the marine boundary layer, and on ice substrates which are relevant to the lowe ...
In recent years, chemometric methods for the analysis of multivariate kinetic data have considerably progressed. Kinetic hard-modelling is one of these methods that is based on the rate law and used to determine the kinetic parameters (e.g. rate constants) ...
The relative basicities of aryllithiums bearing methoxy, chlorine, fluorine, trifluoromethyl and trifluoromethoxy substituents at the ortho, meta, and para positions have been assessed. To this end, two aryllithiums of comparable basicity were equilibrated ...
The kinetics of chlorination of several phenolic compounds and the corresponding formation of chloroform were investigated at room temperature. For the chlorination of phenolic compounds, second-order kinetics was observed, first-order in chlorine, and fir ...
The identification of reaction kinetics involves the determination of a model structure (reaction stoichiometry, rate laws for all reactions) and its corresponding parameters from experimental data. An incremental identification approach for determining th ...
We have investigated different possible mechanisms for the cis-trans isomerization in triply bonded ditungsten complexes with stoichiometry W2Cl4(NHEt)2(PMe3)2 using static d. functional calcns. as well as Car-Parrinello simulations. Our studies reveal an ...
Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibr ...
Abstract: Cross-correlations of rate constants between a system of interest and a better-defined one have become popular as a tool in studying transformations of organic pollutants. A slope of unity (if the correlation is conducted on a log-log basis) in s ...
A general method for the direct evaluation of the temperature dependence of the quantum-mechanical reaction rate constant in many-dimensional systems is described. The method is based on the quantum instanton approximation for the rate constant, thermodyna ...