TY - JOUR
T1 - Static vibrational polarizability of all-trans polyethylene and polysilane
AU - Champagne, Benoît
AU - Perpète, Éric
AU - André, Jean-Marie
AU - Kirtman, Bernard
PY - 1995/12/1
Y1 - 1995/12/1
N2 - The evolution with chain length of the vibrational contribution to the static linear polarizability of all-trans polyethylene and polysilane chains has been computed at the ab initio Hartree-Fock and MP2 levels within the double harmonic oscillator approximation. In polyethylene, the vibrational polarizability per unit cell is very small whereas in polysilane it amount to 50% of its electronic counterpart. The longitudinal component in polysilane mainly originates from one wagging mode and is a consequence of the delocalization due to σ-conjugation. Contrary to polysilane chains, where the local and non-local polarizations induced by the wagging motion of the hydrogen atoms are in phase, these contributions cancel each other in polyethylene chains and result in a very small vibrational polarizability.
AB - The evolution with chain length of the vibrational contribution to the static linear polarizability of all-trans polyethylene and polysilane chains has been computed at the ab initio Hartree-Fock and MP2 levels within the double harmonic oscillator approximation. In polyethylene, the vibrational polarizability per unit cell is very small whereas in polysilane it amount to 50% of its electronic counterpart. The longitudinal component in polysilane mainly originates from one wagging mode and is a consequence of the delocalization due to σ-conjugation. Contrary to polysilane chains, where the local and non-local polarizations induced by the wagging motion of the hydrogen atoms are in phase, these contributions cancel each other in polyethylene chains and result in a very small vibrational polarizability.
UR - http://www.scopus.com/inward/record.url?scp=37049085677&partnerID=8YFLogxK
U2 - 10.1039/FT9959101641
DO - 10.1039/FT9959101641
M3 - Article
AN - SCOPUS:37049085677
SN - 0956-5000
VL - 91
SP - 1641
EP - 1646
JO - Journal of the Chemical Society, Faraday Transactions
JF - Journal of the Chemical Society, Faraday Transactions
IS - 11
ER -