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Issue 3, 2016
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The role of novel Rydberg-valence behaviour in the non-adiabatic dynamics of tertiary aliphatic amines

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Abstract

Time-resolved photoelectron imaging was used to study non-adiabatic relaxation dynamics in N,N-dimethylisopropylamine, N,N-dimethylpropylamine and N-methylpyrrolidine following excitation at 200 nm. This series of tertiary aliphatic amines are all of similar chemical makeup, but exhibit differences in their structure – being branched, straight-chain and cyclic, respectively. Our experimental investigation, supported by extensive theoretical calculations, provides considerable new insight into the nature of the internal conversion processes that mediate dynamical evolution between electronic states of predominantly Rydberg character in this important class of model photochemical systems. In particular, the angle-resolved data afforded by the imaging approach (something not previously reported for tertiary aliphatic amines) offers novel and highly-detailed mechanistic information about the overall relaxation pathway. Strikingly, both the experimental and theoretical findings suggest that a critical factor driving the non-adiabatic dynamics is the evolution of valence character along an N–C stretching coordinate within a member of the 3p manifold. This is in stark contrast to primary and secondary amines, as well as many other small hetero-atom containing organic species, where evolution of valence character within the 3s state is now a well-established phenomenon implicated in mediating ultrafast non-adiabatic photochemistry.

Graphical abstract: The role of novel Rydberg-valence behaviour in the non-adiabatic dynamics of tertiary aliphatic amines

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Publication details

The article was received on 23 Sep 2015, accepted on 26 Nov 2015 and first published on 09 Dec 2015


Article type: Edge Article
DOI: 10.1039/C5SC03616J
Citation: Chem. Sci., 2016,7, 1826-1839
  • Open access: Creative Commons BY license
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    The role of novel Rydberg-valence behaviour in the non-adiabatic dynamics of tertiary aliphatic amines

    J. O. F. Thompson, L. B. Klein, T. I. Sølling, M. J. Paterson and D. Townsend, Chem. Sci., 2016, 7, 1826
    DOI: 10.1039/C5SC03616J

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