TY - JOUR
T1 - Double harmonic vibrational second hyperpolarizabilities of polyyne chains
AU - Perpète, Éric A.
AU - Champagne, Benoît
AU - André, Jean-Marie
AU - Kirtman, Bernard
PY - 1998/2/19
Y1 - 1998/2/19
N2 - The RHF/6-31G longitudinal vibrational second hyperpolarizabilities of increasingly longer polyyne chains have been computed within the double harmonic oscillator approximation. Similarly to polyacetylene, the largest contribution comes from the [α2]0,0 term. About 95% of the latter arises from what we call the quasi-ECC mode. It converges rapidly with chain length to an asymptotic limit slightly (7%) smaller than its static electronic counterpart. The [μβ]0,0 term is negligible. The inclusion of electron correlation within the MP2/6-31G scheme leads to a decrease of the γv/γe ratio by a factor going from roughly 3 for the dimer to 2 for the tetramer.
AB - The RHF/6-31G longitudinal vibrational second hyperpolarizabilities of increasingly longer polyyne chains have been computed within the double harmonic oscillator approximation. Similarly to polyacetylene, the largest contribution comes from the [α2]0,0 term. About 95% of the latter arises from what we call the quasi-ECC mode. It converges rapidly with chain length to an asymptotic limit slightly (7%) smaller than its static electronic counterpart. The [μβ]0,0 term is negligible. The inclusion of electron correlation within the MP2/6-31G scheme leads to a decrease of the γv/γe ratio by a factor going from roughly 3 for the dimer to 2 for the tetramer.
KW - Ab initio quantum chemical calculations
KW - Electronic second hyperpolarizability
KW - Polyyne chains
KW - Vibrational second hyperpolarizability
UR - http://www.scopus.com/inward/record.url?scp=0041856511&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0041856511
SN - 0166-1280
VL - 425
SP - 115
EP - 122
JO - Journal of Molecular Structure: THEOCHEM
JF - Journal of Molecular Structure: THEOCHEM
IS - 1-2
ER -