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

TL;DR

This study uses high-level ab initio methods to clarify the mechanism of a silicon nucleophilic substitution reaction under vibrational strong coupling, revealing new insights into the reaction pathway, electronic effects, and vibrational polariton formation.

Contribution

It provides the first high-level computational analysis of the S_N2 reaction under VSC, identifying a two-step mechanism and the key role of Si-C-stretching vibrational modes.

Findings

Confirmed a two-step reaction mechanism with new encounter complexes

Showed cavity-induced electronic energy corrections are significant

Demonstrated the dominant dipole character of Si-C-stretching mode

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.