TY  - JOUR
TI  - 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
JF  - PHYSICAL CHEMISTRY CHEMICAL PHYSICS
N1  - Export Date: 8 December 2023            
            CODEN: PPCPF            
            Correspondence Address: Papp, D.; MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Rerrich Béla tér 1, Hungary; email: dorapapp@chem.u-szeged.hu            
            Correspondence Address: Czakó, G.; MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Rerrich Béla tér 1, Hungary; email: gczako@chem.u-szeged.hu
AV  - public
IS  - 42
A1  -  Ballay Boldizsar
A1  -  Sz?cs Tímea
A1  -  Papp Dóra
A1  -  Czakó Gábor
SN  - 1463-9076
EP  - 28940
UR  - https://doi.org/10.1039/d3cp03733a
N2  - 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.
ID  - publicatio31846
SP  - 28925
Y1  - 2023///
VL  - 25
ER  -