Circular dichroism of helical structures using semiempirical methods

Research output: Contribution to journalArticle

Abstract

A general semiempirical scheme has been elaborated to simulate circular dichroism (CD) spectra of supramolecular systems. This approach adopts the analytical method of Beck and Hohlneicher [Theor. Chem. Acc. 101, 297 (1999).] to evaluate the one- and two-center integrals over Slater atomic orbitals. The performance of the method, employing INDO/S and CNDO/S semiempirical parametrizations, has been assessed by considering (i) the effect of the size of the singly excited states manifold, (ii) the origin invariance, and (iii) comparisons with the experimental and other theoretical spectra of several helicenes as well as pyridine-pyrimidine oligomers, which can adopt helical conformations. The main results are (i) the INDO/S parametrization with rather small excitation manifolds is able to reproduce, at low computational costs, the experimental CD spectra of several helicenes as well as CD simulations performed at ab initio and time-dependent density functional theory level of approximation; (ii) in the series of homohelicenes, the rotatory strength of the lowest-energy band increases almost linearly with the size of the helix; (iii) as evidenced by the study of tetradodecyloxy helicene bisquinone, packing effects can change the sign of remarkable CD bands, which are used to assign the structure configuration.

Original languageEnglish
Article number204101
JournalThe journal of chemical physics
Volume127
Issue number20
DOIs
Publication statusPublished - 6 Dec 2007

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dichroism
Invariance
Oligomers
Excited states
Band structure
Density functional theory
Conformations
pyrimidines
oligomers
helices
excitation
energy bands
Costs
invariance
pyridines
density functional theory
costs
orbitals
helicenes
configurations

Cite this

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title = "Circular dichroism of helical structures using semiempirical methods",
abstract = "A general semiempirical scheme has been elaborated to simulate circular dichroism (CD) spectra of supramolecular systems. This approach adopts the analytical method of Beck and Hohlneicher [Theor. Chem. Acc. 101, 297 (1999).] to evaluate the one- and two-center integrals over Slater atomic orbitals. The performance of the method, employing INDO/S and CNDO/S semiempirical parametrizations, has been assessed by considering (i) the effect of the size of the singly excited states manifold, (ii) the origin invariance, and (iii) comparisons with the experimental and other theoretical spectra of several helicenes as well as pyridine-pyrimidine oligomers, which can adopt helical conformations. The main results are (i) the INDO/S parametrization with rather small excitation manifolds is able to reproduce, at low computational costs, the experimental CD spectra of several helicenes as well as CD simulations performed at ab initio and time-dependent density functional theory level of approximation; (ii) in the series of homohelicenes, the rotatory strength of the lowest-energy band increases almost linearly with the size of the helix; (iii) as evidenced by the study of tetradodecyloxy helicene bisquinone, packing effects can change the sign of remarkable CD bands, which are used to assign the structure configuration.",
author = "Edith Botek and Benoit Champagne",
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Circular dichroism of helical structures using semiempirical methods. / Botek, Edith; Champagne, Benoit.

In: The journal of chemical physics, Vol. 127, No. 20, 204101, 06.12.2007.

Research output: Contribution to journalArticle

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