Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion

Rasmus Y. Brogaard, Theis I. Sølling, Klaus Braagaard Møller

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The Norrish Type I reaction in the S1 (nπ*) state of acetone is a prototype case of ketone photochemistry. On the basis of results from time-resolved mass spectrometry (TRMS) and photoelectron spectroscopy (TRPES) experiments, it was recently suggested that after excitation the wave packet travels toward the S1 minimum in less than 30 fs and stays there for more than 100 picoseconds [Chem. Phys. Lett.2008, 461, 193]. In this work we present simulated TRMS and TRPES signals based on ab initio multiple spawning simulations of the dynamics during the first 200 fs after excitation, getting quite good agreement with the experimental signals. We can explain the ultrafast decay of the experimental signals in the following manner: the wave packet simply travels, mainly along the deplanarization coordinate, out of the detection window of the ionizing probe. This window is so narrow that subsequent revival of the signal due to the coherent deplanarization vibration is not observed, meaning that from the point of view of the experiment the wave packets travels directly to the S1 minimum. This result stresses the importance of pursuing a closer link to the experimental signal when using molecular dynamics simulations in interpreting experimental results.
Original languageEnglish
JournalJournal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume115
Issue number5
Pages (from-to)556-561
ISSN1089-5639
DOIs
Publication statusPublished - 2011

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