Influence of Intermolecular Interactions on the Reorganization Energy of Charge Transfer between Surface-Attached Dye Molecules
File(s)
Accepted version
Author(s)
Vaissier, V
Frost, JM
Barnes, PRF
Nelson, J
Type
Journal Article
Abstract
The parameters controlling the kinetics of
intermolecular charge transfer are traditionally estimated
from electronic structure calculations on the charge donor
and charge acceptor in isolation. Here, we show that this
procedure results in inaccuracies for hole transfer between a
pair of organic dye molecules by comparing charge-constrained
density functional theory (DFT) calculations on a dye
cation/neutral dye pair to the conventional DFT calculations
on the isolated molecules. We quantify the error made in the
reorganization energy of hole exchange between dye molecules
(λi
). We choose three indolene-based organic dyes with application to dye-sensitized solar cells, namely, D149, D102, and D131,
for which experimental values of λ are available. We find that, although highly system dependent, the intermolecular interaction
between the charge donor and acceptor can lead to a 0.25 eV change in λi
, illustrating the limitations of the widely used original
method in predicting the rate of charge transfer.
intermolecular charge transfer are traditionally estimated
from electronic structure calculations on the charge donor
and charge acceptor in isolation. Here, we show that this
procedure results in inaccuracies for hole transfer between a
pair of organic dye molecules by comparing charge-constrained
density functional theory (DFT) calculations on a dye
cation/neutral dye pair to the conventional DFT calculations
on the isolated molecules. We quantify the error made in the
reorganization energy of hole exchange between dye molecules
(λi
). We choose three indolene-based organic dyes with application to dye-sensitized solar cells, namely, D149, D102, and D131,
for which experimental values of λ are available. We find that, although highly system dependent, the intermolecular interaction
between the charge donor and acceptor can lead to a 0.25 eV change in λi
, illustrating the limitations of the widely used original
method in predicting the rate of charge transfer.
Date Issued
2015-10-29
Date Acceptance
2015-10-05
Citation
JOURNAL OF PHYSICAL CHEMISTRY C, 2015, 119 (43), pp.24337-24341
ISSN
1932-7447
Publisher
AMER CHEMICAL SOC
Start Page
24337
End Page
24341
Journal / Book Title
JOURNAL OF PHYSICAL CHEMISTRY C
Volume
119
Issue
43
Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in JOURNAL OF PHYSICAL CHEMISTRY C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.jpcc.5b09739
Sponsor
The Royal Society
The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
Engineering & Physical Science Research Council (EPSRC)
Grant Number
IF090019/AM
WRMA09FT/HLL
EP/J002305/1
EP/K010298/1
J13361
EP/M025020/1
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Chemistry
Science & Technology - Other Topics
Materials Science
DENSITY-FUNCTIONAL THEORY
SENSITIZED SOLAR-CELLS
ELECTRON-TRANSFER
OXIDE-FILMS
TIO2
MONOLAYERS
TRANSPORT
DYNAMICS
EXCHANGE
Publication Status
Published