Hetero-Diels-Alder and cheletropic additions of sulfur dioxide to 1,2-dimethylidenecycloalkanes. Determination of thermochemical and kinetics parameters for reactions in solution and comparison with estimates from quantum calculations
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The electron self-exchange reaction CrCl(OH2)5(2+) + Cr(OH2)6(2+) -> Cr(OH2)(6)(2+) + CrCl(OH2)(5)(2+), proceeding via the inner-sphere pathway, was investigated with quantum-chemical methods. Geometry and vibrational frequencies of the precursor/successor ...
A straightforward and general way for monitoring chemical reactions is via their thermal signature. Such approach requires however an experimental setup with a high thermal stability that simultaneously allows time-resolved heat detection with high sensiti ...
Extent-based kinetic identification is a modeling technique that uses number of moles / concentrations measurements to compute extents and identify reaction kinetics (partial orders of reactions and reaction rate constant) by the integral method of paramet ...
The torsional barriers of 2'-substituted 2-arylpyridines have been probed experimentally (by using dynamic NMR spectroscopy) and computationally (by using density functional theory). Due to the compressibility of the lone pair, the torsional barriers of th ...
The state-resolved reaction probability of CH4 on Pt(110)-(1×2) was measured as a function of CH4 translational energy for four vibrational eigenstates comprising different amounts of C-H stretch and bend excitation. State-specific reactivity is observed b ...
Naturally occurring intrastrand oxidative crosslink lesions have proven to be a potent source of endogenous DNA damage. Among the variety of lesions that can be formed and have been identified, G[8-5]C damage (in which the C8 atom of a guanine is covalentl ...
The solvation model proposed by Fattebert and Gygi [J. Comput. Chem. 23, 662 (2002)] and Scherlis et al. [J. Chem. Phys. 124, 074103 (2006)] is reformulated, overcoming some of the numerical limitations encountered and extending its range of applicability. ...
Non-linear classical equations of motion may admit degenerate solutions at fixed charges. Whereas the solutions with lower energies are classically stable, those with larger energies are unstable and are referred to as Q-clouds. We consider a theory in whi ...
Despite the widespread use and numerous successful applications of density functional theory, descriptions of hydrocarbon reaction energies remain problematic. Illustrative examples include large underestimation of energies associated with alkane bond sepa ...
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 ...