Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.
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14 April 2012
Research Article|
April 09 2012
Electronic coherence dynamics in trans-polyacetylene oligomers
Ignacio Franco;
Ignacio Franco
a)
1Department of Chemistry,
Northwestern University
, Evanston, Illinois 60208-3113, USA
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Paul Brumer
Paul Brumer
b)
2Chemical Physics Theory Group and Department of Chemistry,
University of Toronto
, Toronto, Ontario M5S 3H6, Canada
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a)
Present address: Theory Department, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany. Electronic mail: franco@fhi-berlin.mpg.de.
b)
Electronic mail: pbrumer@chem.utoronto.ca.
J. Chem. Phys. 136, 144501 (2012)
Article history
Received:
November 28 2011
Accepted:
March 19 2012
Citation
Ignacio Franco, Paul Brumer; Electronic coherence dynamics in trans-polyacetylene oligomers. J. Chem. Phys. 14 April 2012; 136 (14): 144501. https://doi.org/10.1063/1.3700445
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