Journal of Chemical Physics 2011-10-21

Electric field polarization in conventional density functional theory: from quasilinear to two-dimensional and three-dimensional extended systems.

Bernard Kirtman, Valentina Lacivita, Roberto Dovesi, Heribert Reis

Index: J. Chem. Phys. 135(15) , 154101, (2011)

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Abstract

The large overshoot in (hyper)polarizabilities of quasilinear (1D) chains calculated by applying density functional theory with conventional functionals is investigated for several 2D and 3D extended systems. These systems include arrays of molecular hydrogen chains, as well as 2D coronene-type structures and LiF in 1D, 2D, and 3D. Contrary to a recently proposed model it is found that the overshoot persists in all of these cases. A simple explanation is provided by an analysis of the field-induced charges for molecular hydrogen, which shows an excessive buildup at the chain ends regardless of where the chain is located within the 2D and 3D array.© 2011 American Institute of Physics