Imperial College London

Peter Haynes

Faculty of EngineeringDepartment of Materials

Head of Department of Materials
 
 
 
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Contact

 

+44 (0)20 7594 5158p.haynes Website CV

 
 
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Assistant

 

Miss Catherine Graham +44 (0)20 7594 3330

 
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Location

 

201BRoyal School of MinesSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Zuehlsdorff:2016:10.1021/acs.jctc.5b01014,
author = {Zuehlsdorff, TJ and Haynes, PD and Hanke, F and Payne, MC and Hine, ND},
doi = {10.1021/acs.jctc.5b01014},
journal = {Journal of Chemical Theory and Computation},
pages = {1853--1861},
title = {Solvent effects on electronic excitations of an organic chromophore.},
url = {http://dx.doi.org/10.1021/acs.jctc.5b01014},
volume = {12},
year = {2016}
}

RIS format (EndNote, RefMan)

TY  - JOUR
AB - In this work we study the solvatochromic shift of a selected low-energy excited state of alizarin in water by using a linear-scaling implementation of large-scale time-dependent density functional theory (TDDFT). While alizarin, a small organic dye, is chosen as a simple example of solute-solvent interactions, the findings presented here have wider ramifications for the realistic modeling of dyes, paints, and pigment-protein complexes. We find that about 380 molecules of explicit water need to be considered in order to yield an accurate representation of the solute-solvent interaction and a reliable solvatochromic shift. By using a novel method of constraining the TDDFT excitation vector, we confirm that the origin of the slow convergence of the solvatochromic shift with system size is due to two different effects. The first factor is a strong redshift of the excitation due to an explicit delocalization of a small fraction of the electron and the hole from the alizarin onto the water, which is mainly confined to within a distance of 7 Å from the alizarin molecule. The second factor can be identified as long-range electrostatic influences of water molecules beyond the 7 Å region on the ground-state properties of alizarin. We also show that these electrostatic influences are not well reproduced by a QM/MM model, suggesting that full QM studies of relatively large systems may be necessary in order to obtain reliable results.
AU - Zuehlsdorff,TJ
AU - Haynes,PD
AU - Hanke,F
AU - Payne,MC
AU - Hine,ND
DO - 10.1021/acs.jctc.5b01014
EP - 1861
PY - 2016///
SN - 1549-9626
SP - 1853
TI - Solvent effects on electronic excitations of an organic chromophore.
T2 - Journal of Chemical Theory and Computation
UR - http://dx.doi.org/10.1021/acs.jctc.5b01014
UR - http://www.ncbi.nlm.nih.gov/pubmed/26967019
UR - http://hdl.handle.net/10044/1/31011
VL - 12
ER -