application of the Coulomb and Helmholtz Green's functions
smoothing of the potential and initial guess
manual evaluation of the solution along a line
Background
The Hartree-Fock wave function is computed for the helium atom in three dimensions without using spherical symmetry.
The atomic orbital is an eigenfunction of the Fock operator
that depends upon the orbital via the Coulomb potential ( ) arising from the electronic density ( ).
Implementation
Per the usual MADNESS practice, the equation is rearranged into integral form
where and is the Green's function for the Helmholtz equation
The initial guess is , which is normalized before use. Each iteration proceeds by
computing the density by squaring the orbital,
computing the Coulomb potential by applying the Coulomb Green's function,
multiplying the orbital by the total potential,
updating the orbital by applying the Helmholtz Green's function,
updating the energy according to a second-order accurate estimate (see the initial MRQC paper), and finally
normalizing the new wave function.
The kinetic energy operator is denoted by . Thus, one would expect to compute the kinetic energy with respect to a wave function by . In this particular example, the wave functions goes to zero smoothly before the boundary so we apply the product rule for differentiation and the kinetic energy is equal to .