Nucleophilic substitution at silicon under vibrational strong coupling: Refined insights from a high-level ab initio perspective

Abstract: We study the bimolecular nucleophilic substitution (S$\mathrm{N}$2) reaction of 1-phenyl-2-trimethylsilylacetylene (PTA) under vibrational strong coupling (VSC) from the perspective of high-level ab initio quantum and polaritonic chemistry. Specifically, we address conflicting mechanistic proposals, cavity-induced electronic corrections under VSC and the relevance of a previously debated Si-C-stretching motion of PTA for vibrational polariton formation. We first provide computational evidence for a two-step mechanism based on density functional theory and high-level coupled cluster results, identify new encounter and products complexes and illustrate the relevance of diffuse basis functions for a qualitatively correct description of anionic reactive systems. We subsequently show that cavity-induced dipole fluctuation corrections of electronic energies can be significant on the level of cavity Born-Oppenheimer coupled cluster theory and discuss their qualitative impact on the proposed two-step mechanism taking into account cavity-induced molecular reorientation. We finally show that the Si-C-stretching contribution to the experimentally relevant double-peak feature of PTA exhibits a dominant dipole character, which renders it central for linear IR response and vibrational polariton formation despite the presence of CH$_3$-rocking contributions. The dipole character along the cleaving Si-C-bond is eventually shown to rationalize Rabi splittings throughout the proposed two-step mechanism. Our work refines the microscopic perspective on the S$\mathrm{N}$2 reaction of PTA under VSC and highlights recent developments in ab initio polaritonic chemistry for the VSC regime.