Vibrational raman optical activity as a mean for revealing the helicity of oligosilanes: a quantum chemical investigation.
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.
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles, 61, B-5000 Namur, Belgium. vincent.liegeois@fundp.ac.be
Vincent
V
Liégeois
Olivier
O
Quinet
Benoît
B
Champagne