Geometry, dipole moment, polarizability and first hyperpolarizability of polymethineimine: An assessment of electron correlation contributions
Authors:
- 1 September 2004
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 121 (9) , 4389-4396
Abstract
We have investigated the geometries as well as the longitudinal dipole moment (μ), polarizability (α), and first hyperpolarizability (β) of polymethineimine oligomers using different approaches [Hartree–Fock (HF), second-order Møller–Plesset (MP2), and hybrid density functional theory (DFT) methods (B3LYP and PBE0)] for evaluating the geometries and the nonlinear optical properties. It turns out that (i) HF and the selected DFT methods provide the incorrect sign for β of short and medium size oligomers. (ii) The B3LYP and PBE0 electron correlation correction are too small for μ, too large for α, and for some oligomer lengths, they are in the wrong direction for β. (iii) On the contrary to polyacetylene, the hybrid-DFT geometries are in poor agreement with MP2 geometries; the former showing much smaller bond length alternations.Keywords
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