Energy Transfer Mechanisms in Large Low-Bandgap Polymers from Time-Resolved Experiments and Nonadiabatic Molecular Dynamics Calculations

02 May 2025, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Conjugated polymers offer unprecedented chemical tunability for modulating energy transfer in a multitude of infrared light applications. In this work, we use a combination of time-resolved spectroscopic experiments and nonadiabatic molecular dynamics calculations to probe the photochemistry and nonradiative transitions in a recently synthesized narrow bandgap donor-acceptor conjugated polymer based on alternating cyclopentadithiophene and electronegative benzothiadiazole heterocycles. Using large-scale semi-empirical nonadiabatic molecular dynamics, which can treat a large 260-atom hexamer, we calculate an S5 --> S1 lifetime of 34.75 fs, which is consistent with our time-resolved spectroscopic data. Our simulations suggest that vibronic motions of the central carbons in the cyclopentadithiophenes functional groups are predominantly involved in the nonradiative transitions and the excitation becomes more localized on a monomer fragment over time. The combined use of time-resolved experiments and nonadiabatic molecular dynamics calculations in this work provide mechanistic insight into chemical functionalities that can be tuned to enhance energy transfer in other prospective low-bandgap polymer materials.

Keywords

polymer
time-resolved spectroscopy
nonadiabatic molecular dynamics
photochemistry
nonradiative transitions
vibronic
energy transfer
donor-acceptor
low bandgap

Supplementary materials

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Description
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Title
Supplementary Material
Description
Visualization of the nonadiabatic derivative coupling vectors and transition densities at geometries where nonradiative transitions occur.
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