Energy Flow and Fragmentation Dynamics of N,N-Dimethylisopropylamine
The energy flow and fragmentation dynamics of N,N-dimethylisopropylamine (DMIPA) upon excitation to the 3p Rydberg states has been investigated with use of time-resolved photoelectron and mass spectrometry. The 3p states are short-lived, with a lifetime of 701 ± 45 fs. From the time dependence of th...
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Published in | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 12; pp. 4251 - 4255 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
30.03.2006
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Subjects | |
Online Access | Get full text |
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Summary: | The energy flow and fragmentation dynamics of N,N-dimethylisopropylamine (DMIPA) upon excitation to the 3p Rydberg states has been investigated with use of time-resolved photoelectron and mass spectrometry. The 3p states are short-lived, with a lifetime of 701 ± 45 fs. From the time dependence of the photoelectron spectra, we infer that the primary reaction channel leads to the 3s level, which itself decays to the ground state with a decay time of 87.9 ± 10.2 ps. The mass spectrum reveals fragmentation with cleavage at the α C−C bond, indicating that the energy deposited in vibrations during the internal conversion from 3p to 3s exceeds the bond energy. A thorough examination of the binding energies and temporal dynamics of the Rydberg states, as well as a comparison to the related fragmentation of N,N-dimethyl-2-butanamine (DM2BA), suggests that the fragments are formed on the ion surfaces, i.e., after ionization and on a time scale much slower than the fluorescence decay from 3s to the ground state. |
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Bibliography: | istex:3D2FC52B5701696001887D21FAD7DD3EF9761A93 ark:/67375/TPS-RP6NQP45-4 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp0574706 |