Collect. Czech. Chem. Commun. 2008, 73, 1509-1524

Calculations of Polarizabilities and Their Gradients for Electron Energy-Loss Spectroscopy

Ivana Paidarováa, Roman Čuríka,* and Stephan P. A. Sauerb

a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejškova 3, 182 23 Prague 8, Czech Republic
b Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark


We illustrate for a set of small hydrocarbons, CH4, C2H4, C3H6 and C3H8, the important role of the electric dipole polarizability tensor and its geometric derivatives in theoretical models of electron energy-loss spectra (EELS). The coupled cluster linear response method together with Sadlej's polarized valence triple zeta basis set of atomic orbitals were used to calculate the polarizabilities and polarizability gradients. Incorporation of these ab initio data into the discrete momentum representation method (DMR) leads to perfect agreement between theory and collision experiments.

Keywords: Geometric derivatives of the electric dipole polarizability tensor; Coupled clusters linear response method; Electron energy-loss spectra; Discrete momentum representation method; DFT calculations; Hydrocarbons.

References: 95 live references.