relation: http://publicatio.bibl.u-szeged.hu/31846/ title: Phosphorus-centered ion-molecule reactions: benchmark ab initio characterization of the potential energy surfaces of the X<SUP>-</SUP> + PH<sub>2</sub>Y [X, Y = F, Cl, Br, I] systems creator: Ballay Boldizsar creator: Szűcs Tímea creator: Papp Dóra creator: Czakó Gábor subject: 01.04. Kémiai tudományok description: In the present work we determine the benchmark relative energies and geometries of all the relevant stationary points of the X- + PH2Y [X, Y = F, Cl, Br, I] identity and non-identity reactions using state-of-the-art electronic-structure methods. These phosphorus-centered ion-molecule reactions follow two main reaction routes: bimolecular nucleophilic substitution (S(N)2), leading to Y- + PH2X, and proton transfer, resulting in HX + PHY- products. The S(N)2 route can proceed through Walden-inversion, front-side-attack retention, and double-/multiple-inversion pathways. In addition, we also identify the following product channels: H--formation, PH2-- and PH2-formation, (PH)-P-1- and (PH)-P-3-formation, H-2-formation and HY + PHX- formation. The benchmark classical relative energies are obtained by taking into account the core-correlation, scalar relativistic, and post-(T) corrections, which turn out to be necessary to reach subchemical (<1 kcal mol(-1)) accuracy of the results. Classical relative energies are augmented with zero-point-energy contributions to gain the benchmark adiabatic energies. date: 2023 type: Folyóiratcikk type: PeerReviewed format: text identifier: http://publicatio.bibl.u-szeged.hu/31846/1/PCCP_25_28925_2023.pdf identifier: Ballay Boldizsar; Szűcs Tímea; Papp Dóra; Czakó Gábor: Phosphorus-centered ion-molecule reactions: benchmark ab initio characterization of the potential energy surfaces of the X<SUP>-</SUP> + PH<sub>2</sub>Y [X, Y = F, Cl, Br, I] systems. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 25 (42). pp. 28925-28940. ISSN 1463-9076 (2023) identifier: doi:10.1039/d3cp03733a relation: https://doi.org/10.1039/d3cp03733a relation: 34240025 language: eng relation: info:eu-repo/semantics/altIdentifier/doi/10.1039/d3cp03733a rights: info:eu-repo/semantics/openAccess