Analyzing molecular static linear response properties with perturbed localized orbitals.
Perturbed localized molecular orbitals (LMOs), correct to first order in an applied static perturbation and consistent with a chosen localization functional, are calculated using analytic derivative techniques. The formalism is outlined for a general static perturbation and variational localization functionals. Iterative and (formally) single-step approaches are compared. The implementation employs an iterative sequence of 2x2 orbital rotations. The procedure is verified by calculations of molecular electric-field perturbations. Boys LMO contributions to the electronic static polarizability and the electric-field perturbation of the r(2) expectation value are calculated and analyzed for ethene, ethyne, and fluoroethene (H(2)C=CHF). For ethene, a comparison is made with results from a Pipek-Mezey localization. The calculations show that a chemically intuitive decomposition of the calculated properties is possible with the help of the LMO contributions and that the polarizability contributions in similar molecules are approximately transferable.[1]References
- Analyzing molecular static linear response properties with perturbed localized orbitals. Autschbach, J., King, H.F. J. Chem. Phys (2010) [Pubmed]
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