Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon ...Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.展开更多
The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coin...The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.12325406,92261201,12404305,and W2512072)the Shaanxi Province Natural Science Fundamental Research Project (Grant Nos.2023JC-XJ-03 and23JSQ013)the China Postdoctoral Science Foundation (Grant Nos.BX20240286 and 2024M7625)。
文摘Abiotic oxygen formation predates photosynthesis,sustaining early chemical evolution,yet its elementary mechanisms remain contested.Here,we show the production pathways for molecular oxygen from doubly ionized carbon dioxide upon electron-impact.Through fragment ions and electron coincidence momentum imaging,we unambiguously determine the ionization mechanism by measuring the projectile energy loss in association with the C^(+) +O_(2)^(+) channel.Further potential energy and trajectory calculations enable us to elucidate the dynamical details of this fragmentation process,in which a bond rearrangement pathway is found to proceed via the structural deformation to a triangular intermediate.Moreover,we demonstrate a further roaming pathway for the formation of O_(2)^(+) from CO_(2)^(+) 2,in which a frustrated C-O bond cleavage leaves the O atom without sufficient energy to escape.The O atom then wanders around varied configuration spaces of the flat potential energy regions and forms a C-O-O_(2)^(+) intermediate prior to the final products C^(+) +O_(2)^(+).Considering the large quantities of free electrons in interstellar space,the processes revealed here are expected to be significant and should be incorporated into atmospheric evolution models.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12325406,92261201,12404305,11974272)the Shannxi Province Natural Science Fundamental Research Project(Grant Nos.2023JC-XJ-03 and 23JSQ013)the Fundamental Research Funds for the Central Universities(Grant No.xzy022024040)。
文摘The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.
