Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules

dc.contributor.author

Hu, X

dc.contributor.author

Xiao, D

dc.contributor.author

Keinan, S

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Asselberghs, I

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Therien, MJ

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Clays, K

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Yang, W

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Beratan, DN

dc.date.accessioned

2011-06-21T17:26:44Z

dc.date.issued

2010-02-11

dc.description.abstract

Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in materials science and electronic structure theory. We show that the generalized Thomas-Kuhn sum rules, combined with linear absorption data and measured hyperpolarizability at one or two frequencies, may be used to predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and three-level contributions that arise from the lowest two or three excited electronic state manifolds, enabling us to describe the unusual observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores, where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the high oscillator strength transition dipoles of these components in a head-to-tail arrangement. We show that some of these structures can possess very similar linear absorption spectra yet manifest dramatically different frequency dependent hyperpolarizabilities, because of three-level contributions that result from excited state-to excited state transition dipoles among charge polarized states. Importantly, this approach provides a quantitative scheme to use linear optical absorption spectra and very limited individual hyperpolarizability measurements to predict the entire frequency-dependent nonlinear optical response. Copyright © 2010 American Chemical Society.

dc.description.version

Version of Record

dc.identifier.eissn

1932-7455

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1932-7447

dc.identifier.uri

https://hdl.handle.net/10161/4078

dc.language.iso

en_US

dc.publisher

American Chemical Society (ACS)

dc.relation.ispartof

Journal of Physical Chemistry C

dc.relation.isversionof

10.1021/jp911556x

dc.relation.journal

Journal of Physical Chemistry C

dc.title

Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules

dc.title.alternative
dc.type

Journal article

duke.contributor.orcid

Therien, MJ|0000-0003-4876-0036

duke.contributor.orcid

Beratan, DN|0000-0003-4758-8676

duke.date.pubdate

2010-2-11

duke.description.issue

5

duke.description.volume

114

pubs.begin-page

2349

pubs.end-page

2359

pubs.issue

5

pubs.organisational-group

Basic Science Departments

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Biochemistry

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Biomedical Engineering

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Chemistry

pubs.organisational-group

Duke

pubs.organisational-group

Duke Cancer Institute

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Institutes and Centers

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Physics

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Pratt School of Engineering

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School of Medicine

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Trinity College of Arts & Sciences

pubs.publication-status

Published

pubs.volume

114

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