Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules
Repository Usage Stats
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.
Published Version (Please cite this version)10.1021/jp911556x
Publication InfoHu, 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.
More InfoShow full item record
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
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
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.
Alphabetical list of authors with Scholars@Duke profiles.