We performed extensive quasiclassical trajectory calculations for the H+C_(2)D_(2)→HD+C_(2)D/D_(2)+C_(2)H reaction based on a recently developed,global and accurate potential energy surface by the fundamental-invaria...We performed extensive quasiclassical trajectory calculations for the H+C_(2)D_(2)→HD+C_(2)D/D_(2)+C_(2)H reaction based on a recently developed,global and accurate potential energy surface by the fundamental-invariant neural network method.The direct abstraction pathway plays a minor role in the overall reactivity,which can be negligible as compared with the roaming pathways.The acetylenefacilitated roaming pathway dominates the reactivity,with very small contributions from the vinylidene-facilitated roaming.Although the roaming pathways proceed via the short-lived or long-lived complex forming process,the computed branching ratio of product HD to D_(2) is not far away from 2:1,implying roaming dynamics for this reaction is mainly contributed from the long-lived complex-forming process.The resulting angular distributions for the two product channels are also quite different.These computational results give valuable insights into the significance and isotope effects of roaming dynamics in the biomolecular reactions.展开更多
The dissociative chemisorption of N_(2) is the rate-limiting step for ammonia synthesis in industry.Here,we investigated the role of initially vibrational excitation and ro-tational excitation of N_(2) for its reactiv...The dissociative chemisorption of N_(2) is the rate-limiting step for ammonia synthesis in industry.Here,we investigated the role of initially vibrational excitation and ro-tational excitation of N_(2) for its reactivity on the Fe(111)surface,based on a recently developed six-dimensional potential energy surface.Six-dimensional quantum dynamics study was carried out to investi-gate the effect of vibrational excitation for incidence energy below 1.6 eV,due to sig-nificant quantum effects for this reaction.The effects of vibrational and rotational excitations at high incidence energies were revealed by quasiclassical trajectory calculations.We found that raising the translational energy can enhance the dissociation probability to some extent,however,the vibrational excitation or rotational excitation can promote disso-ciation more efficiently than the same amount of translational energy.This study provides valuable insight into the mode-specific dynamics of this heavy diatom-surface reaction.展开更多
基金supported by the National Natural Science Foundation of China(No.22173099 and No.12174044)Liao Ning Revitalization Talents Program(XLYC1907190)。
文摘We performed extensive quasiclassical trajectory calculations for the H+C_(2)D_(2)→HD+C_(2)D/D_(2)+C_(2)H reaction based on a recently developed,global and accurate potential energy surface by the fundamental-invariant neural network method.The direct abstraction pathway plays a minor role in the overall reactivity,which can be negligible as compared with the roaming pathways.The acetylenefacilitated roaming pathway dominates the reactivity,with very small contributions from the vinylidene-facilitated roaming.Although the roaming pathways proceed via the short-lived or long-lived complex forming process,the computed branching ratio of product HD to D_(2) is not far away from 2:1,implying roaming dynamics for this reaction is mainly contributed from the long-lived complex-forming process.The resulting angular distributions for the two product channels are also quite different.These computational results give valuable insights into the significance and isotope effects of roaming dynamics in the biomolecular reactions.
基金supported by the National Key R&D Program of China(No.2018YFE0203003)the National Natural Science Foundation of China(No.22173099 and No.22173101)the Liaoning Revitalization Talents Program(No.XLYC1907190)。
文摘The dissociative chemisorption of N_(2) is the rate-limiting step for ammonia synthesis in industry.Here,we investigated the role of initially vibrational excitation and ro-tational excitation of N_(2) for its reactivity on the Fe(111)surface,based on a recently developed six-dimensional potential energy surface.Six-dimensional quantum dynamics study was carried out to investi-gate the effect of vibrational excitation for incidence energy below 1.6 eV,due to sig-nificant quantum effects for this reaction.The effects of vibrational and rotational excitations at high incidence energies were revealed by quasiclassical trajectory calculations.We found that raising the translational energy can enhance the dissociation probability to some extent,however,the vibrational excitation or rotational excitation can promote disso-ciation more efficiently than the same amount of translational energy.This study provides valuable insight into the mode-specific dynamics of this heavy diatom-surface reaction.