Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes: A quantum chemical investigation

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Using theoretical simulations based on Hartree-Fock and density-functional theory calculations, the simulated vibrational Raman optical activity spectra of helical conformers of heptasilane are shown to present signatures sensitive to the helicity. These signatures are associated with collective wagging, twisting, and rocking motions. These simulated spectra have been obtained by combining analytical and numerical differentiation procedures to evaluate the geometry derivatives of the optical tensors entering into the expressions of the vibrational Raman optical activity intensities. From an investigation of basis set and electron correlation effects, it is shown that, like for local vibrations, diffuse functions are compulsory for evaluating the vibrational Raman optical activity intensities of collective vibrational motions.
langue originaleAnglais
journalJournal of chemical physics
Volume122
Numéro de publication21
Les DOIs
étatPublié - 1 juin 2005

Empreinte digitale

Electron correlations
optical activity
Density functional theory
Tensors
Derivatives
Geometry
signatures
numerical differentiation
twisting
tensors
density functional theory
vibration
geometry
electrons
simulation

Citer ceci

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abstract = "Using theoretical simulations based on Hartree-Fock and density-functional theory calculations, the simulated vibrational Raman optical activity spectra of helical conformers of heptasilane are shown to present signatures sensitive to the helicity. These signatures are associated with collective wagging, twisting, and rocking motions. These simulated spectra have been obtained by combining analytical and numerical differentiation procedures to evaluate the geometry derivatives of the optical tensors entering into the expressions of the vibrational Raman optical activity intensities. From an investigation of basis set and electron correlation effects, it is shown that, like for local vibrations, diffuse functions are compulsory for evaluating the vibrational Raman optical activity intensities of collective vibrational motions.",
author = "Vincent Li{\'e}geois and O. Quinet and B. Champagne",
note = "Copyright 2012 Elsevier B.V., All rights reserved.",
year = "2005",
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T1 - Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes

T2 - A quantum chemical investigation

AU - Liégeois, Vincent

AU - Quinet, O.

AU - Champagne, B.

N1 - Copyright 2012 Elsevier B.V., All rights reserved.

PY - 2005/6/1

Y1 - 2005/6/1

N2 - Using theoretical simulations based on Hartree-Fock and density-functional theory calculations, the simulated vibrational Raman optical activity spectra of helical conformers of heptasilane are shown to present signatures sensitive to the helicity. These signatures are associated with collective wagging, twisting, and rocking motions. These simulated spectra have been obtained by combining analytical and numerical differentiation procedures to evaluate the geometry derivatives of the optical tensors entering into the expressions of the vibrational Raman optical activity intensities. From an investigation of basis set and electron correlation effects, it is shown that, like for local vibrations, diffuse functions are compulsory for evaluating the vibrational Raman optical activity intensities of collective vibrational motions.

AB - Using theoretical simulations based on Hartree-Fock and density-functional theory calculations, the simulated vibrational Raman optical activity spectra of helical conformers of heptasilane are shown to present signatures sensitive to the helicity. These signatures are associated with collective wagging, twisting, and rocking motions. These simulated spectra have been obtained by combining analytical and numerical differentiation procedures to evaluate the geometry derivatives of the optical tensors entering into the expressions of the vibrational Raman optical activity intensities. From an investigation of basis set and electron correlation effects, it is shown that, like for local vibrations, diffuse functions are compulsory for evaluating the vibrational Raman optical activity intensities of collective vibrational motions.

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DO - 10.1063/1.1914769

M3 - Article

VL - 122

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

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