Using geometrical optimization and DFT method at the B3LYP/6-31G （d） level, nineteen equilibrium geometries were identified, and three transition states of dissociation reaction of C3O6 clusters were also found. The...Using geometrical optimization and DFT method at the B3LYP/6-31G （d） level, nineteen equilibrium geometries were identified, and three transition states of dissociation reaction of C3O6 clusters were also found. The vibrational frequencies and intrinsic reaction coordinate （IRC） verification at the same level were computed to verify the transitions. And then we calculated the dissociation energies and analyzed the dissociation channels. The computational results show that the dissociation energies of C3O6 isomers relative to three CO2 are between 1.509 × 103 and 10.61 × 10^3 kJ·kg^-1, and the energy barriers of the reactions are 92.857, 131.138 and 185.793 kJ·mol^-1. Both the high dissociation energies and high energy barriers show that C3O6 clusters studied in this paper are stable enough to be used as high-energy-density materials.展开更多
We report a study on photo-ionization of benzene and aniline with incidental subsequent dissociation by the customized reflection time-of-flight mass spectrometer utilizing a deep ultraviolet 177.3 nm laser.Highly eff...We report a study on photo-ionization of benzene and aniline with incidental subsequent dissociation by the customized reflection time-of-flight mass spectrometer utilizing a deep ultraviolet 177.3 nm laser.Highly efficient ionization of benzene is observed with a weak C4H3+fragment formed by undergoing disproportional C-C bond dissociation.In comparison,a major C5H6+·fragment and a minor C6H6+·radical are produced in the ionization of aniline pertaining to the removal of CNH·and NH·radicals,respectively.First-principles calculation is employed to reveal the photo-dissociation pathways of these two molecules having a structural difference of just an amino group.It is demonstrated that hydrogen atom transfer plays an important role in the cleavage of C-C or C-N bonds in benzene and aniline ions.This study is helpful to understand the underlying mechanisms of chemical bond fracture of benzene ring and related aromatic molecules.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.92261113 and No.21722308)Key Project of Frontier Science Research of Chinese Academy of Sciences(QYZDB-SSWSLH024).
基金Supported by the Natural Science Foundation of Shandong Province (No. Y2006B24 and Y2008B33)
文摘Using geometrical optimization and DFT method at the B3LYP/6-31G （d） level, nineteen equilibrium geometries were identified, and three transition states of dissociation reaction of C3O6 clusters were also found. The vibrational frequencies and intrinsic reaction coordinate （IRC） verification at the same level were computed to verify the transitions. And then we calculated the dissociation energies and analyzed the dissociation channels. The computational results show that the dissociation energies of C3O6 isomers relative to three CO2 are between 1.509 × 103 and 10.61 × 10^3 kJ·kg^-1, and the energy barriers of the reactions are 92.857, 131.138 and 185.793 kJ·mol^-1. Both the high dissociation energies and high energy barriers show that C3O6 clusters studied in this paper are stable enough to be used as high-energy-density materials.
基金supported by the National Natural Science Foundation of China(No.91536105,No.11174186,No.21722308)the National Project Development of Advanced Scientific Instruments Based on Deep Ultraviolet Laser Source(No.Y31M0112C1)+2 种基金the Beijing Natural Science Foundation(No.2192064)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(No.QYZDB-SSW-SLH024)financial support from the Tianshan Scholar Program。
文摘We report a study on photo-ionization of benzene and aniline with incidental subsequent dissociation by the customized reflection time-of-flight mass spectrometer utilizing a deep ultraviolet 177.3 nm laser.Highly efficient ionization of benzene is observed with a weak C4H3+fragment formed by undergoing disproportional C-C bond dissociation.In comparison,a major C5H6+·fragment and a minor C6H6+·radical are produced in the ionization of aniline pertaining to the removal of CNH·and NH·radicals,respectively.First-principles calculation is employed to reveal the photo-dissociation pathways of these two molecules having a structural difference of just an amino group.It is demonstrated that hydrogen atom transfer plays an important role in the cleavage of C-C or C-N bonds in benzene and aniline ions.This study is helpful to understand the underlying mechanisms of chemical bond fracture of benzene ring and related aromatic molecules.
