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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C4CP04571H· OSTI ID:1233177
 [1];  [1];  [2];  [1]
  1. Univ. of Leeds (United Kingdom)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations

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.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
EP/I014500/1; EP/J001481/1; CHE1124515; AC03-76SF00515
OSTI ID:
1233177
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 17, Issue 5; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 61 works
Citation information provided by
Web of Science

References (44)

Solving the time-dependent Schrödinger equation for nuclear motion in one step: direct dynamics of non-adiabatic systems journal August 2008
Probing ultrafast dynamics in photoexcited pyrrole: timescales for 1πσ* mediated H-atom elimination journal January 2013
Nonadiabatic dynamics with the help of multiconfigurational Ehrenfest method: Improved theory and fully quantum 24D simulation of pyrazine journal June 2010
The ultraviolet photodissociation dynamics of pyrrole journal September 1994
Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics journal August 2014
On-the-fly ab initio molecular dynamics with multiconfigurational Ehrenfest method journal December 2012
Controlling the mechanism of fulvene S1/S0 decay: switching off the stepwise population transfer journal January 2010
Exploring nuclear motion through conical intersections in the UV photodissociation of phenols and thiophenol journal July 2008
Excited Electronic States and Nonadiabatic Effects in Contemporary Chemical Dynamics journal August 2009
Ab Initio Multiple Spawning Dynamics of Excited Butadiene: Role of Charge Transfer journal November 2009
Time resolved velocity map imaging of H-atom elimination from photoexcited imidazole and its methyl substituted derivatives journal January 2011
The Role of   * Excited States in the Photodissociation of Heteroaromatic Molecules journal June 2006
Multi-Electronic-State Molecular Dynamics:  A Wave Function Approach with Applications journal January 1996
Thermochemistry and Electronic Structure of the Pyrrolyl Radical journal October 2004
Detailed Balance in Ehrenfest Mixed Quantum-Classical Dynamics journal January 2006
Simulation of ultrafast photodynamics of pyrrole with a multiconfigurational Ehrenfest method journal January 2013
Exploring Ultrafast H-Atom Elimination versus Photofragmentation Pathways in Pyrazole Following 200 nm Excitation journal August 2011
Photoinduced multi-mode quantum dynamics of pyrrole at the – conical intersections journal August 2007
Exploiting temporal nonlocality to remove scaling bottlenecks in nonadiabatic quantum dynamics journal March 1999
Implementation of ab initio multiple spawning in the Molpro quantum chemistry package journal May 2008
Non-adiabatic dynamics of pyrrole: Dependence of deactivation mechanisms on the excitation energy journal September 2010
Basis set sampling in the method of coupled coherent states: Coherent state swarms, trains, and pancakes journal February 2008
Photochemistry of pyrrole: Time-dependent quantum wave-packet description of the dynamics at the π1σ*-S0 conical intersections journal October 2005
Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol journal June 2005
Photodissociation and photoionization of pyrrole following the multiphoton excitation at 243 and 364.7 nm
  • van den Brom, Alrik. J.; KapeliosDepartment of Chemistry, Un, Makis; Kitsopoulos, Theofanis N.
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 5 https://doi.org/10.1039/b415766d
journal January 2005
High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of pyrrole journal January 2004
Near-UV photolysis of substituted phenols : Part II. 4-, 3- and 2-methylphenol journal January 2008
Excited-state hydrogen detachment and hydrogen transfer driven by repulsive 1πσ* states: A new paradigm for nonradiative decay in aromatic biomolecules journal February 2002
Near ultraviolet photolysis of deuterated pyrrole journal January 2006
High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of phenol journal October 2006
Multiconfigurational Ehrenfest approach to quantum coherent dynamics in large molecular systems journal January 2011
Time-dependent quantum wave-packet description of the 1 πσ* photochemistry of pyrrole journal January 2004
Quantum mechanics with the basis set guided by Ehrenfest trajectories: Theory and application to spin-boson model journal June 2009
Molecular dynamics with electronic transitions journal July 1990
Optimization of width parameters for quantum dynamics with frozen Gaussian basis sets journal May 2010
Photodissociation dynamics of pyrrole: Evidence for mode specific dynamics from conical intersections journal January 2004
Investigation of multiple electronic excited state relaxation pathways following 200 nm photolysis of gas-phase imidazole journal January 2012
Femtosecond evolution of the pyrrole molecule excited in the near part of its UV spectrum journal August 2012
UV photodissociation of N-methylpyrrole: The role of 1πσ∗ states in non-hydride heteroaromatic systems journal May 2008
DNA Excited-State Dynamics: From Single Bases to the Double Helix journal May 2009
Exploring the mechanisms of H atom loss in simple azoles: Ultraviolet photolysis of pyrazole and triazole journal February 2010
High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of imidazole journal November 2006
Ultraviolet photolysis of adenine: Dissociation via the π1σ* state journal March 2007
Data associated with 'Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging' dataset January 2018

Cited By (10)

The quantum chemistry of attosecond molecular science journal July 2019
Ultrafast photodissociation dynamics of 2-ethylpyrrole: adding insight to experiment with ab initio multiple cloning journal January 2019
Ultrafast photodissociation dynamics of pyrazole, imidazole and their deuterated derivatives using ab initio multiple cloning journal January 2019
A two-layer approach to the coupled coherent states method journal January 2016
Photodissociation dynamics in the first absorption band of pyrrole. I. Molecular Hamiltonian and the Herzberg-Teller absorption spectrum for the A21(πσ*)←X̃1 A1(ππ) transition journal March 2018
Photodissociation dynamics in the first absorption band of pyrrole. II. Photofragment distributions for the 1 A2(πσ*)←X̃1A1(ππ) transition journal March 2018
The effect of sampling techniques used in the multiconfigurational Ehrenfest method journal May 2018
A walk through the approximations of ab initio multiple spawning journal April 2018
Perspective: The development and applications of H Rydberg atom translational spectroscopy methods journal August 2018
Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks journal March 2019

Figures / Tables (6)

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