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

Vincent Liégeois; O. Quinet; B. Champagne

doi:10.1063/1.1914769

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

Vincent Liégeois, O. Quinet, B. Champagne

Research output: Contribution to journal › Article

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.

Original language	English
Journal	Journal of chemical physics
Volume	122
Issue number	21
DOIs	https://doi.org/10.1063/1.1914769
Publication status	Published - 1 Jun 2005

Fingerprint

Electron correlations

optical activity

Density functional theory

Tensors

Derivatives

Geometry

signatures

numerical differentiation

twisting

tensors

density functional theory

vibration

geometry

electrons

simulation

Cite this

Liégeois, V., Quinet, O., & Champagne, B. (2005). Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes: A quantum chemical investigation. Journal of chemical physics, 122(21). https://doi.org/10.1063/1.1914769

Liégeois, Vincent ; Quinet, O. ; Champagne, B. / Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes : A quantum chemical investigation. In: Journal of chemical physics. 2005 ; Vol. 122, No. 21.

@article{096af8d3a92b49c1be5b4e5e04b42651,

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

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",

year = "2005",

month = "6",

day = "1",

doi = "10.1063/1.1914769",

language = "English",

volume = "122",

journal = "The journal of chemical physics",

issn = "0021-9606",

publisher = "American Institute of Physics Publising LLC",

number = "21",

}

Liégeois, V , Quinet, O & Champagne, B 2005, 'Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes: A quantum chemical investigation', Journal of chemical physics, vol. 122, no. 21. https://doi.org/10.1063/1.1914769

Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes : A quantum chemical investigation. / Liégeois, Vincent ; Quinet, O.; Champagne, B.

In: Journal of chemical physics, Vol. 122, No. 21, 01.06.2005.

Research output: Contribution to journal › Article

TY - JOUR

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.

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.

UR - http://www.scopus.com/inward/record.url?scp=21244474014&partnerID=8YFLogxK

U2 - 10.1063/1.1914769

DO - 10.1063/1.1914769

M3 - Article

AN - SCOPUS:21244474014

VL - 122

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

IS - 21

ER -

Liégeois V , Quinet O , Champagne B. Vibrational Raman optical activity as a mean for revealing the helicity of oligosilanes: A quantum chemical investigation. Journal of chemical physics. 2005 Jun 1;122(21). https://doi.org/10.1063/1.1914769