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The calculation of static polarizabilities of 1-3D periodic compounds. the implementation in the crystal code

Authors

  • Mauro Ferrero,

    1. Dipartimento di Chimica IFM, Università di Torino and NIS—Nanostructured Interfaces and Surfaces—Centre of Excellence, Via P. Giuria 7, 10125 Torino, Italy
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  • Michel Rérat,

    1. Equipe de Chimie Physique, IPREM UMR5254, Université de Pau, 64000 Pau, France
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  • Roberto Orlando,

    Corresponding author
    1. Dipartimento di Scienze e Tecnologie Avanzate, Università del Piemonte Orientale, Via Bellini 25/G, 15100 Alessandria, Italy
    • Dipartimento di Scienze e Tecnologie Avanzate, Università del Piemonte Orientale, Via Bellini 25/G, 15100 Alessandria, Italy
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  • Roberto Dovesi

    1. Dipartimento di Chimica IFM, Università di Torino and NIS—Nanostructured Interfaces and Surfaces—Centre of Excellence, Via P. Giuria 7, 10125 Torino, Italy
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Abstract

The Coupled Perturbed Hartree–Fock (CPHF) scheme has been implemented in the CRYSTAL06 program, that uses a gaussian type basis set, for systems periodic in 1D (polymers), 2D (slabs), 3D (crystals) and, as a limiting case, 0D (molecules), which enables comparison with molecular codes. CPHF is applied to the calculation of the polarizability α of LiF in different aggregation states: finite and infinite chains, slabs, and cubic crystal. Correctness of the computational scheme for the various dimensionalities and its numerical efficiency are confirmed by the correct trend of α: α for a finite linear chain containing N LiF units with large N tends to the value for the infinite chain, N parallel chains give the slab value when N is sufficiently large, and N superimposed slabs tend to the bulk value. CPHF results compare well with those obtained with a saw-tooth potential approach, previously implemented in CRYSTAL. High numerical accuracy can easily be achieved at relatively low cost, with the same kind of dependence on the computational parameters as for the SCF cycle. Overall, the cost of one component of the dielectric tensor is roughly the same as for the SCF cycle, and it is dominated by the calculation of two-electron four-center integrals. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008

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