Issue 38, 2022

The ultrafast vibronic dynamics of ammonia's [D with combining tilde] state

Abstract

Using vacuum-ultraviolet time-resolved velocity map imaging of photoelectrons, we study ultrafast coupled electronic and nuclear dynamics in low-lying Rydberg states of ammonia. Vibrationally-resolved internal vibrational relaxation (IVR) is observed in a progression of the e′ bending modes. This vibrational progression is only observed in the [D with combining tilde] state, and is lost upon ultrafast internal conversion to the [C with combining tilde] and [B with combining tilde] electronic states. Due to the ultrashort time scale of the internal conversion (ca. 64 fs), and the vibronic resolution, the non-adiabatic coupling vectors are identified and verified with ab initio calculations. The time-scale of this IVR process is highly surprising and significant because IVR is usually treated as an incoherent process that proceeds statistically, according to a “Fermi's Golden Rule”-like model, where the process scales with the available degrees of freedom. Here, we show that it can be highly non-statistical, restricted to only a very small subset of vibrational motions.

Graphical abstract: The ultrafast vibronic dynamics of ammonia's  [[D with combining tilde]]  state

Supplementary files

Article information

Article type
Paper
Submitted
08 Jul 2022
Accepted
14 Sep 2022
First published
14 Sep 2022
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2022,24, 23340-23349

The ultrafast vibronic dynamics of ammonia's [D with combining tilde] state

M. D. J. Waters and H. J. Wörner, Phys. Chem. Chem. Phys., 2022, 24, 23340 DOI: 10.1039/D2CP03117E

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