The impact of chemical structure and molecular packing on the electronic polarisation of fullerene arrays
File(s)FewChiaTeo_PCCP_2017_JustAccepted.pdf (7.76 MB)
Accepted version
Author(s)
Few, SPM
Chia, C
Teo, D
Kirkpatrick, J
Nelson, J
Type
Journal Article
Abstract
Electronic polarisation contributes to the electronic landscape as seen by separating charges in organic materials. The nature of electronic polarisation depends on the polarisability, density, and arrangement of polarisable molecules. In this paper, we introduce a microscopic, coarse-grained model in which we treat each molecule as a polarisable site, and use an array of such polarisable dipoles to calculate the electric field and associated energy of any arrangement of charges in the medium. The model incorporates chemical structure via the molecular polarisability and molecular packing patterns via the structure of the array. We use this model to calculate energies of charge pairs undergoing separation in finite fullerene lattices of different chemical and crystal structures. The effective dielectric constants that we estimate from this approach are in good quantitative agreement with those measured experimentally in C60 and phenyl-C61-butyric acid methyl ester (PCBM) films, but we find significant differences in dielectric constant depending on packing and on direction of separation, which we rationalise in terms of density of polarisable fullerene cages in regions of high field. In general, we find lattices containing molecules of more isotropic polarisability tensors exhibit higher dielectric constants. By exploring several model systems we conclude that differences in molecular polarisability (and therefore, chemical structure) appear to be less important than differences in molecular packing and separation direction in determining the energetic landscape for charge separation. We note that the results are relevant for finite lattices, but not necessarily for infinite systems. We propose that the model could be used to design molecular systems for effective electronic screening.
Date Issued
2017-06-23
Date Acceptance
2017-06-22
Citation
Physical Chemistry Chemical Physics, 2017, 19, pp.18709-18720
ISSN
1463-9084
Publisher
Royal Society of Chemistry
Start Page
18709
End Page
18720
Journal / Book Title
Physical Chemistry Chemical Physics
Volume
19
Copyright Statement
© the Owner Societies 2017
Sponsor
Engineering & Physical Science Research Council (E
Grant Number
J13361
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
ORGANIC SOLAR-CELLS
POLYFLUORENE COPOLYMER/FULLERENE BLENDS
CHARGE-TRANSFER EXCITONS
OPEN-CIRCUIT VOLTAGE
BULK HETEROJUNCTIONS
CARRIER GENERATION
OPTICAL-PROPERTIES
FIELD DEPENDENCE
TRANSFER STATES
DYNAMICS
02 Physical Sciences
03 Chemical Sciences
Chemical Physics
Publication Status
Published