Predicting solvatochromic shifts and colours of a solvated organic dye: the example of nile red
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Supporting information
Accepted version
Author(s)
Zuehlsdorff, TJ
Haynes, PD
Payne, MC
Hine, NDM
Type
Journal Article
Abstract
The solvatochromic shift, as well as the change in colour of the simple organic dye nile red, is studied in two polar and two non-polar solvents in the context of large-scale time-dependent density-functional theory (TDDFT) calculations treating large parts of the solvent environment from first principles. We show that an explicit solvent representation is vital to resolve absorption peak shifts between nile red in n-hexane and toluene, as well as acetone and ethanol. The origin of the failure of implicit solvent models for these solvents is identified as being due to the strong solute-solvent interactions in form of π-stacking and hydrogen bonding in the case of toluene and ethanol. We furthermore demonstrate that the failures of the computationally inexpensive Perdew-Burke-Ernzerhof (PBE) functional in describing some features of the excited state potential energy surface of the S1 state of nile red can be corrected for in a straightforward fashion, relying only on a small number of calculations making use of more sophisticated range-separated hybrid functionals. The resulting solvatochromic shifts and predicted colours are in excellent agreement with experiment, showing the computational approach outlined in this work to yield very robust predictions of optical properties of dyes in solution.
Date Issued
2017-03-30
Date Acceptance
2017-03-14
Citation
Journal of Chemical Physics, 2017, 146
ISSN
1089-7690
Publisher
AIP Publishing
Journal / Book Title
Journal of Chemical Physics
Volume
146
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering and Physical Sciences Research Council
Grant Number
EP/J015059/1
EP/G036888/1
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
DENSITY-FUNCTIONAL THEORY
POLARIZABLE CONTINUUM MODEL
ELECTRONIC EXCITATIONS
MOLECULAR-DYNAMICS
OPTICAL-PROPERTIES
SPECTRA
SOLVENTS
APPROXIMATION
FLUORESCENCE
ABSORPTION
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
124504