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

Publication: Research - peer-reviewJournal article – Annual report year: 2011

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Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion. / Brogaard, Rasmus Y.; Sølling, Theis I.; Møller, Klaus Braagaard.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 115, No. 5, 2011, p. 556-561.

Publication: Research - peer-reviewJournal article – Annual report year: 2011

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Brogaard, Rasmus Y.; Sølling, Theis I.; Møller, Klaus Braagaard / Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 115, No. 5, 2011, p. 556-561.

Publication: Research - peer-reviewJournal article – Annual report year: 2011

Bibtex

@article{7be8214162554b29ac5b118f473aa232,
title = "Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion",
publisher = "American Chemical Society",
author = "Brogaard, {Rasmus Y.} and Sølling, {Theis I.} and Møller, {Klaus Braagaard}",
year = "2011",
doi = "10.1021/jp1084197",
volume = "115",
number = "5",
pages = "556--561",
journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",
issn = "1089-5639",

}

RIS

TY - JOUR

T1 - Initial Dynamics of The Norrish Type I Reaction in Acetone: Probing Wave Packet Motion

A1 - Brogaard,Rasmus Y.

A1 - Sølling,Theis I.

A1 - Møller,Klaus Braagaard

AU - Brogaard,Rasmus Y.

AU - Sølling,Theis I.

AU - Møller,Klaus Braagaard

PB - American Chemical Society

PY - 2011

Y1 - 2011

N2 - 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.

AB - 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.

U2 - 10.1021/jp1084197

DO - 10.1021/jp1084197

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 5

VL - 115

SP - 556

EP - 561

ER -