Chemical Reactivity
in the Gas Phase and in Solution
| We are carrying out computational studies of structure and reactivity of organic and organometallic species using ab initio quantum chemical methods and statistical mechanical simulation techniques. These studies range from electronic structure calculations to simulations of the effect of solvation on the rate of chemical transformations. Recently, Yirong Mo developed a computational method, which enforces some of the electrons in a molecule to be localized, computationally, within a specific region of the system. Using this technique, which is termed as the Block-Localized Wave function (BLW) method, he is able to determine properties such as resonace energies and charge transfer interactions. Findings from these calculations are of importance for understanding the nature of chemical bonding as well as for developing potential energy functions for condensed phase simulations. The following two examples illustrate some of the applications of the BLW method. |
Cation-p Interactions:
| An interesting finding from recent studies of cation-p interactions is that charge transfer occurs with the transfer of p electrons of the benzene ring into the empty orbitals of the cation, whereas polarization interaction takes place via a mechanism of charge migration from the in-plane C-H s bonds into the p* orbitals. Electron density difference (EDD) plots, made possible by the BLW method, vividly depict these electronic effects. |
Charge Transfer Polarization