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Title: Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging

Abstract

In this study, we report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropic component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum.

Authors:
 [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Leeds (United Kingdom)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1233177
Grant/Contract Number:  
EP/I014500/1; EP/J001481/1; CHE1124515; AC03-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 17; Journal Issue: 5; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Makhov, Dmitry V., Saita, Kenichiro, Martinez, Todd J., and Shalashilin, Dmitrii V. Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging. United States: N. p., 2014. Web. doi:10.1039/C4CP04571H.
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Makhov, Dmitry V., Saita, Kenichiro, Martinez, Todd J., & Shalashilin, Dmitrii V. Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging. United States. https://doi.org/10.1039/C4CP04571H
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Makhov, Dmitry V., Saita, Kenichiro, Martinez, Todd J., and Shalashilin, Dmitrii V. Thu . "Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging". United States. https://doi.org/10.1039/C4CP04571H. https://www.osti.gov/servlets/purl/1233177.
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@article{osti_1233177,
title = {Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging},
author = {Makhov, Dmitry V. and Saita, Kenichiro and Martinez, Todd J. and Shalashilin, Dmitrii V.},
abstractNote = {In this study, we report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropic component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum.},
doi = {10.1039/C4CP04571H},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 5,
volume = 17,
place = {United States},
year = {Thu Dec 11 00:00:00 EST 2014},
month = {Thu Dec 11 00:00:00 EST 2014}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/C4CP04571H
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Cited by: 61 works
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Figures / Tables:

Fig. 1 Fig. 1: A sketch of the AIMC propagation scheme. First the wave function is represented as a superposition of Gaussian Coherent States (‘‘bits’’), each of which is a central trajectory for a train basis set. After passing the intersection the trains branch in the process of cloning (a similar diagrammore » would apply to MCE, without the cloning step).« less
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Data associated with 'Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging'
dataset, January 2018

  • Makhov, Dmitry; Saita, Kenichiro; Martinez, Todd
  • University of Leeds
  • DOI: 10.5518/425
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