Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2006-03-30

Energy flow and fragmentation dynamics of n,n-dimethylisopropylamine.

Jaimie L Gosselin, Michael P Minitti, Fedor M Rudakov, Theis I Sølling, Peter M Weber

Index: J. Phys. Chem. A 110(12) , 4251-5, (2006)

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Abstract

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 alpha 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.