Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules
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.
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https://hdl.handle.net/10161/4078Published Version (Please cite this version)
10.1021/jp911556xPublication Info
Hu, X; Xiao, D; Keinan, S; Asselberghs, I; Therien, MJ; Clays, K; ... Beratan, DN (2010). Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis
of absorption data and thomas-kuhn sum rules. Journal of Physical Chemistry C, 114(5). pp. 2349-2359. 10.1021/jp911556x. Retrieved from https://hdl.handle.net/10161/4078.This is constructed from limited available data and may be imprecise. To cite this
article, please review & use the official citation provided by the journal.
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Show full item recordScholars@Duke
David N. Beratan
R.J. Reynolds Distinguished Professor of Chemistry
Dr. Beratan is developing theoretical approaches to understand the function of complex
molecular and macromolecular systems, including: the molecular underpinnings of energy
harvesting and charge transport in biology; the mechanism of solar energy capture
and conversion in man-made structures; the nature of charge conductivity in naturally
occurring nucleic acids and in synthetic constructs, including the photochemical repair
of damaged DNA in extremophiles; CH bond activation by copper oxygenas
Michael J. Therien
William R. Kenan, Jr. Distinguished Professor of Chemistry
Our research involves the synthesis of compounds, supramolecular assemblies, nano-scale
objects, and electronic materials with unusual ground-and excited-state characteristics,
and interrogating these structures using state-of-the-art transient optical, spectroscopic,
photophysical, and electrochemical methods. Over chemical dimensions that span molecules
to materials, we probe experimental and theoretical aspects of charge migration reactions
and ultrafast electron transfer processes. Insights
Weitao Yang
Philip Handler Distinguished Professor of Chemistry
Prof. Yang, the Philip Handler Professor of Chemistry, is developing methods for quantum
mechanical calculations of large systems and carrying out quantum mechanical simulations
of biological systems and nanostructures. His group has developed the linear scaling
methods for electronic structure calculations and more recently the QM/MM methods
for simulations of chemical
reactions in enzymes.
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