We present a detailed analysis of the anomalous carbocations by (a) probing electronic structural properties, (b) <i>ab initio</i> dynamics simulations over a range of internal energies, (c) analysis of reduced dimensional potential surfaces directed along selected conformational transition pathways, (d) dynamically averaged vibrational spectra computed from <i>ab initio</i> dynamics trajectories, and (e) two-dimensional time–frequency analysis to probe conformational dynamics. Key findings are as follows: (i) It appears that these non-classical carbocations are stabilized by delocalized nuclear frameworks and “proton shuttles”. (ii) The vibrational signatures are complex and in many cases dominated by multiple isomers arising from classical as well as non-classical arrangements.

“Grotthuss-like” proton relays in anomalous carbocations dictate spectroscopy, stability and mechanisms: Case studies on small and medium sized non-classical hydrocarbons along with deuterated counterparts

256th National Meeting (2018)

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