Self-consistent methods constrained to a fixed number of particles in a given fragment and its relation to the electronegativity equalization method

A. Cedillo, D. Van Neck, P. Bultinck
Theoretical Chemistry Accounts
131(6), 1227


The variational procedure of the Hartree–Fock and Kohn–Sham methods can be modified by adding one or more constraints that fix the number of electrons in a given number of molecular fragments. The corresponding Euler–Lagrange equations lead to a modified Fock matrix, where the contribution from the constraints only depends on the overlap matrix, when using the Mulliken or Hirshfeld atoms-in-molecules method. For all compounds in the test set, the energy shows a quadratic dependence on the fixed charges. This behavior provides a procedure to obtain the atomic electronegativity and hardness parameters in the
electronegativity equalization method.