Nucleophilic substitution at silicon under vibrational strong coupling: Refined insights from a high-level ab initio perspective
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arXiv
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| Natura: | Preprint |
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2026
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| _version_ | 1866917240729763840 |
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| author | Frerick, Niels-Ole Roemelt, Michael Fischer, Eric W. |
| author_facet | Frerick, Niels-Ole Roemelt, Michael Fischer, Eric W. |
| contents | 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}$2 reaction of PTA under VSC and highlights recent developments in ab initio polaritonic chemistry for the VSC regime. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_18540 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Nucleophilic substitution at silicon under vibrational strong coupling: Refined insights from a high-level ab initio perspective Frerick, Niels-Ole Roemelt, Michael Fischer, Eric W. Chemical Physics We study the bimolecular nucleophilic substitution (S$_\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. |
| title | Nucleophilic substitution at silicon under vibrational strong coupling: Refined insights from a high-level ab initio perspective |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2601.18540 |