Ultrafast structural pathway of charge transfer in n, n, n ′, n ′-tetramethylethylenediamine

Xinxin Cheng, Yao Zhang, Yan Gao, Hannes Jónsson, Peter M. Weber*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

We have explored the ultrafast molecular structural dynamics associated with charge transfer in N,N,N′,N′-tetramethylethylenediamine using Rydberg fingerprint spectroscopy in conjunction with self-interaction corrected density functional theory. Excitation at 239 nm prepares the molecule in the Franck-Condon region of the 3s state with the charge localized on one of the two amine groups. As seen from the time-dependent Rydberg electron binding energies, the pathway of the rapidly ensuing dynamics leads through several structurally distinct conformers with various degrees of charge localization before reaching the fully charge-delocalized structure on a picosecond time scale. At several steps along the reaction path, the transient structures are identified through a comparison of the spectroscopically observed binding energies with computed values. The molecular structure is seen to evolve dynamically from an initially folded conformer to the stretched form that supports charge delocalization before an equilibrium sets in with forward and backward time constants of 1.19 (0.14) and 2.61 (0.31) ps, respectively. A coherent wavepacket motion in the charge-localized state with a period of 270 (17) fs and damping of 430 (260) fs is observed and tentatively assigned to the nitrogen umbrella motion. The damping time constant indicates the rate of the energy flow into other vibrations that are not activated by the optical excitation.

Original languageEnglish
Pages (from-to)2813-2818
Number of pages6
JournalJournal of Physical Chemistry A
Volume119
Issue number12
DOIs
Publication statusPublished - 26 Mar 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

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