Electron Density Dynamics in the Electronic Ground State: Motion Along the Kekulé Mode of Benzene
Schild, Axel and Choudhary, Deepanshu and Sambre, Vaibhav D. and Paulus, Beate – 2012
If the Born–Oppenheimer approximation is invoked for the description of chemical reactions, the electron density rearranges following the motion of the nuclei. Even though this approach is central to theoretical chemistry, the explicit time dependence of the electron density is rarely studied, especially if the nuclei are treated quantum mechanically. In this article, we model the motion of benzene along the Kekulé vibrational coordinate to simulate the nuclear dynamics and electron density dynamics in the electronic ground state. Details of the change of core, valence, and π electrons are determined and analyzed. We show how the pictures anticipated by drawing Lewis structures of the rearrangement correlate with the time-dependent quantum description of the process.