63 research outputs found
Splitting âintervocalicâ: Expanding the typology of lenition environments
The basic types of lenition environments (âinitialâ, âintervocalicâ, âfinalâ) need to be separately evaluated as they differ along parameters like word position (e.g., pre-consonantal vs. final codas) or stress relations. This paper argues that we need to recognise an additional such parameter: the length of the vowel preceding an intervocalic consonant. We show that a number of phenomena from varieties of English and German show lenition patterns which draw a distinction between reflexes found in post-short (vc) and post-long (vvc) environments. The theoretical consequence of our observations is that phonological theory needs to be able to account for the post-short vs. post-long distinction in the form of a parametrically-determined representational difference
Density functional theory study of the multimode Jahn-Teller effect â ground state distortion of benzene cation
The multideterminental-DFT approach performed to analyze Jahn-Teller (JT) active molecules is described. Extension of this method for the analysis of the adiabatic potential energy surfaces and the multimode JT effect is presented. Conceptually a simple model, based on the analogy between the JT distortion and reaction coordinates gives further information about microscopic origin of the JT effect. Within the harmonic approximation the JT distortion can be expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation, which allows calculating the Intrinsic Distortion Path, IDP, exactly from the high symmetry nuclear configuration to the low symmetry energy minimum. It is possible to quantify the contribution of different normal modes to the distortion, their energy contribution to the total stabilization energy and how their contribution changes along the IDP. It is noteworthy that the results obtained by both multideterminental-DFT and IDP methods for different classes of JT active molecules are consistent and in agreement with available theoretical and experimental values. As an example, detailed description of the ground state distortion of benzene cation is given
Sodium ion interactions with aqueous glucose: Insights from quantum mechanics, molecular dynamics, and experiment
In the last several decades, significant efforts have been conducted to understand the fundamental reactivity of glucose derived from plant biomass in various chemical environments for conversion to renewable fuels and chemicals. For reactions of glucose in water, it is known that inorganic salts naturally present in biomass alter the product distribution in various deconstruction processes. However, the molecular-level interactions of alkali metal ions and glucose are unknown. These interactions are of physiological interest as well, for example, as they relate to cation-glucose cotransport. Here, we employ quantum mechanics (QM) to understand the interaction of a prevalent alkali metal, sodium, with glucose from a structural and thermodynamic perspective. The effect on B-glucose is subtle: a sodium ion perturbs bond lengths and atomic partial charges less than rotating a hydroxymethyl group. In contrast, the presence of a sodium ion significantly perturbs the partial charges of ñ-glucose anomeric and ring oxygens. Molecular dynamics (MD) simulations provide dynamic sampling in explicit water, and both the QM and the MD results show that sodium ions associate at many positions with respect to glucose with reasonably equivalent propensity. This promiscuous binding nature of Na + suggests that computational studies of glucose reactions in the presence of inorganic salts need to ensure thorough sampling of the cation positions, in addition to sampling glucose rotamers. The effect of NaCl on the relative populations of the anomers is experimentally quantified with light polarimetry. These results support the computational findings that Na + interacts similarly with a- and B-glucose
Adenine versus guanine quartets in aqueous solution: dispersion-corrected DFT study on the differences in Ï-stacking and hydrogen-bonding behavior
Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 1. Reaction of Methanol with Fluorine Atoms
Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 2. Reaction of Methanol with Chlorine and Bromine Atoms
Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals
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