Observation of Structural Wavepacket Motion: The Umbrella Mode in Rydberg-Excited N-Methyl Morpholine

Yao Zhang, Sanghamitra Deb, Hannes Jónsson, Peter M. Weber*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)


We have observed time-resolved, structural dynamics of a coherent vibrational wavepacket in Rydberg-excited N-methyl morpholine, a molecule with 48 internal degrees of freedom. The molecular structure was established by associating the time-dependent Rydberg electron binding energy, obtained from time-resolved photoionization-photoelectron spectroscopy, to the molecular structure using self-interaction corrected density functional calculations. Optical excitation at 226 nm launches an oscillatory wavepacket in the amine umbrella coordinate with a 650 fs period. Even though the Franck-Condon excitation is at an angle of 17°, the wavepacket settles into an oscillation between 4° and -10° within a fraction of a vibrational period and then dephases with a time constant of 750 fs.

Original languageEnglish
Pages (from-to)3740-3744
Number of pages5
JournalJournal of Physical Chemistry Letters
Issue number16
Publication statusPublished - 17 Aug 2017

Bibliographical note

Funding Information:
This study was supported by the National Science Foundation (Grant Number CBET-1336105) and by the Icelandic Science Fund. This research was conducted using computational resources and services at the Center for Computation and Visualization, Brown University.

Publisher Copyright:
© 2017 American Chemical Society.


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