Energy profiles, molecular modelling

The effects of the solvent and finite temperature (entropy) on the Wittig reaction have been studied by using DFT in combination with molecular dynamics and a continuum solvation model.62 The free energy profile has been found to have a significant entropic barrier to the addition step of the reaction where only a small barrier was present in the potential energy curve. 

The free energy profile for the electron transfer reaction in a polar solvent is examined based on the extended reference interaction site method (ex-RISM) applying it to a simple model of a charge separation reaction which was previously studied by Carter and Hynes with molecular dynamics simulations. Due to the non-linear nature of the hypemetted chain (HNC) closure to solve the RISM equation, our method can shed light on the non-linearity of the free energy profiles, and we discuss these problems based on the obtained free energy profile. 

In the Sumi-Marcus (SM) model 13a], the perspective is changed, with a TST rate constant based on a low-frequency molecular mode (m) as the reaction coordinate, and with G dependent on a diffusive solvent coordinate X. For ease of comparison with other models, we transform X (relative to its definition in [13a]) so as to correspond to a continuous charging parameter (X = 0 for the bottom of the reactant well, and X = 1 for the bottom of the product well for the case of parabolic free energy profiles the transformation is linear the more general situation is dealt with in [98]). Also, 7.ci = A + z , and /.d = a, , where 7, , is the reorganization energy associated with the low-frequency mode m. These definitions lead to the following equation ... 

At the time the CLAP force field was proposed, many of the existing ionic liquid models used to borrow parameters from different, not always compatible, sources. For instance, it was common to see parameterizations of the cation and of the anion using information from different force fields [10,11,13], In the development of the CLAP force-field, in order to respect internal consistency, ab initio calculations were used extensively to provide essential data for the development of an internally consistent force field. This included molecular geometry optimization and the description of electron density using extended basis sets, leading to the evaluation of force field parameters such as torsion energy profiles and electrostatic charges on the interaction centers. 

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