Nuclear quantum effect and H/D isotope effect on Cl· + (H₂O)_n→ HCl + OH·(H₂O)_n−1(n= 1–3) reactions

Abstract

Cl·+ (H2O)n → HCl + OH(H2O)n−1 (n = 1–3) reactions have been investigated using multicomponent quantum mechanics method, which can take account of the nuclear quantum effect of proton and deuteron.

Multicomponent QM study on the reaction of HOSO + NO2 with H2O: Nuclear quantum effect on structure and reaction energy profile

“…We have already demonstrated that MC_QM-CI-NEB approach adequately provides effective TS structure on the MC_QM PES for various chemical reactions. [24,27,28] 3 | COMPUTATIONAL DETAIL…”

“…If ∇V ( R i ) values are evaluated by MC_QM calculations, we can obtain both minimum energy path and TS structure on the MC_QM effective PES by minimizing (CI‐)NEB forces in Equation . We have already demonstrated that MC_QM‐CI‐NEB approach adequately provides effective TS structure on the MC_QM PES for various chemical reactions …”

“…Also, we can represent various interesting H/D isotope effect with the aid of MC_QM method, since the H/D isotope effect is attributed to the difference of NQE between proton and deuteron. Quite recently, we successfully elucidated the importance of NQE of hydrogen nucleus in hydrogen transfer reactions of Cl• + (H 2 O) n ( n = 1‐3) using MC_QM‐climbing image‐nudged elastic band (CI‐NEB) method . In this study, we would like to analyze the reaction of HOSO + NO 2 with and without H 2 O including the NQE of hydrogen nuclei using our MC_QM method.…”

“…Quite recently, we successfully elucidated the importance of NQE of hydrogen nucleus in hydrogen transfer reactions of Cl• + (H 2 O) n (n = 1-3) using MC_QM-climbing image-nudged elastic band (CI-NEB) method. [24] In this study, we would like to analyze the reaction of HOSO + NO 2 with and without H 2 O including the NQE of hydrogen nuclei using our MC_QM method. H/D isotope effects on geometries, reaction energy profiles, and interaction energies were also analyzed with the aid of the MC_QM method.…”

Kinetics of the OH+HCl→H2O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling

“…The anisotropic forces generated by electrostatic and dispersion interactions between reactants promote the formation of the wells in the entrance channels in the PES. However, differently from the entrance channel complex (HO‐‐‐HX), the origin of stability of the exit channel complex (X‐‐‐H 2 O) cannot be explained by electrostatic or dispersion interactions, since neither the geometry nor the energy encodes with this type of interactions. Ref.…”