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Macroscopic polarization from electronic wave functions
Author(s) -
Resta Raffaele
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)75:4/5<599::aid-qua25>3.0.co;2-8
Subject(s) - polarization (electrochemistry) , wave function , observable , dipole , physics , quantum mechanics , uncorrelated , atomic orbital , geometric phase , periodic boundary conditions , boundary value problem , electron , chemistry , mathematics , statistics
The dipole moment of any finite and neutral system, having a square‐integrable wave function, is a well‐defined quantity. The same quantity is ill‐defined for an extended system, whose wave function invariably obeys periodic (Born–von Kármán) boundary conditions. Despite this fact, macroscopic polarization is a theoretically accessible quantity, for either uncorrelated or correlated many‐electron systems: in both cases, polarization is a rather “exotic” observable. For an uncorrelated—either Hartree–Fock or Kohn–Sham—crystalline solid, polarization has been expressed and computed as a Berry phase of the Bloch orbitals (since 1993). The case of a correlated and/or disordered system received a definitive solution only very recently (1998): This latest development allows us to present here the whole theory from a novel, and very general, viewpoint. The modern theory of polarization is even relevant to the foundations of density functional theory in extended systems. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 599–606, 1999