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_N2) 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 product 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 at 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 a linear IR response and vibrational polariton formation despite the presence of CH₃-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_N2 reaction of PTA under VSC and highlights recent developments in ab initio polaritonic chemistry for the VSC regime.