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On the Interplay Between Chirality and Exciton Coupling: A DFT Calculation of the Circular Dichroism in π ‐Stacked Ethylene
Author(s) -
Norman Patrick,
Linares Mathieu
Publication year - 2014
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22331
Subject(s) - chirality (physics) , chemistry , exciton , circular dichroism , molecular physics , monomer , chemical physics , density functional theory , ethylene , propagator , polarization (electrochemistry) , vibrational circular dichroism , optical rotation , circular polarization , crystallography , polymer , condensed matter physics , computational chemistry , chiral symmetry , optics , physics , quantum mechanics , biochemistry , organic chemistry , nambu–jona lasinio model , catalysis , quark , microstrip
The chirality of stacked weakly interacting π ‐systems was interpreted in terms of Frenkel exciton states and the formation of excitonic circular dichroism (CD) bands was monitored for ethylene stacks of varying sizes. Convergence of CD bands with respect to the system size was observed for stacks involving around 10 molecules. By means of rotation around the C–C double bond in ethylene, chirality was induced in the monomeric system and which was shown to dominate the spectral responses, even for polymer aggregates. In helical assemblies of chiral entities, there will always be a mix of excitonic and monomeric contributions to the CD signal and it is demonstrated that the complex polarization propagator approach in combination with Density Functional Theory is a suitable method to address this situation. Chirality 26:483–489, 2014 . © 2014 Wiley Periodicals, Inc.