Imperial College London
Alternate

ProfessorPatriciaHunt

Faculty of Natural Sciences, Department of Chemistry

Visiting Professor
 
 
 
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Contact

 

p.hunt Website

 
 
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Location

 

Molecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Heid:2018:10.1039/c7cp08549d,
author = {Heid, E and Hunt, PA and Schroeder, C},
doi = {10.1039/c7cp08549d},
journal = {Physical Chemistry Chemical Physics},
pages = {8554--8563},
title = {Evaluating excited state atomic polarizabilities of chromophores},
url = {http://dx.doi.org/10.1039/c7cp08549d},
volume = {20},
year = {2018}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Ground and excited state dipoles and polarizabilities of the chromophores N-methyl-6-oxyquinolinium betaine (MQ) and coumarin 153 (C153) in solution have been evaluated using time-dependent density functional theory (TD-DFT). A method for determining the atomic polarizabilities has been developed; the molecular dipole has been decomposed into atomic charge transfer and polarizability terms, and variation in the presence of an electric field has been used to evaluate atomic polarizabilities. On excitation, MQ undergoes very site-specific changes in polarizability while C153 shows significantly less variation. We also conclude that MQ cannot be adequately described by standard atomic polarizabilities based on atomic number and hybridization state. Changes in the molecular polarizability of MQ (on excitation) are not representative of the local site-specific changes in atomic polarizability, thus the overall molecular polarizability ratio Image ID:c7cp08549d-t1.gif does not provide a good approximation for local atom-specific polarizability changes on excitation. Accurate excited state force fields are needed for computer simulation of solvation dynamics. The chromophores considered in this study are often used as molecular probes. The methods and data reported here can be used for the construction of polarizable ground and excited state force fields. Atomic and molecular polarizabilities (ground and excited states) have been evaluated over a range of functionals and basis sets. Different mechanisms for including solvation effects have been examined; using a polarizable continuum model, explicit solvation and via sampling of clusters extracted from a MD simulation. A range of different solvents have also been considered.
AU  - Heid,E
AU  - Hunt,PA
AU  - Schroeder,C
DO  - 10.1039/c7cp08549d
EP  - 8563
PY  - 2018///
SN  - 1463-9076
SP  - 8554
TI  - Evaluating excited state atomic polarizabilities of chromophores
T2  - Physical Chemistry Chemical Physics
UR  - http://dx.doi.org/10.1039/c7cp08549d
UR  - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000428779700018&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - http://hdl.handle.net/10044/1/65384
VL  - 20
ER  -
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