Water mediated hydrogen abstraction mechanism in the radical reaction between HOSO and NO2

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

“…In particular, the activation barrier vanishes in MC_QM (H) result by including NQE of proton. This result is in good agreement with the zero‐point vibrational energy‐corrected CBS‐QB3 energy profile, in which the activation barrier of the reaction with one H 2 O molecule is only 0.1 kcal/mol. It should be mentioned here that only zero‐point vibrational energies are included in the previous CBS‐QB3 calculation, while not only protonic kinetic energy but also the relaxation of electronic structure and geometrical parameters are taken into account in our MC_QM calculations.…”

“…Let us summarize the reaction profile of HOSO + NO 2 with one water molecule briefly. In the present study, we have analyzed the water‐mediated hydrogen‐relay mechanism (reaction ( b )) in addition to the previously reported hydrogen transfer reaction (reaction ( a )) . Our MC_QM calculations revealed that the stationary point structures in hydrogen‐relay mechanism have lower energies compared to the corresponding stationary point structures in direct hydrogen transfer mechanism.…”

“…The hydrogen migrations from HOSO to H 2 O and from H 2 O to NO 2 proceed in concert. It should be noted here that Lesar analyzed only reaction ( a ) …”

“…Thus, not only SO 2 and NO x themselves, but also the reactions concerning SO 2 and NO x have been attracted a lot of attention in atmospheric chemistry. Several groups have earnestly studied both experimentally and theoretically …”

“…Several groups have earnestly studied both experimentally and theoretically. [2][3][4][5][6][7] Lesar and coworkers analyzed the hydrogen transfer reaction between HOSO and NO 2 using the highly-accurate CBS-QB3 and G2MP2 theoretical methods. They have analyzed the reaction pathways leading to trans-HONO and HOSO 2 , and have revealed that the reaction leading to trans-HONO is energetically preferred.…”