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Hartree-Fock Theory Hartree-Fock theory Morten Hjorth-Jensen1 National Superconducting Cyclotron Laboratory and Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824, USA1 May 16-20 2016 c 2013-2016, Morten Hjorth-Jensen. Released under CC Attribution-NonCommercial 4.0 license Why Hartree-Fock? Hartree-Fock (HF) theory is an algorithm for finding an approximative expression for the ground state of a given Hamiltonian. The basic ingredients are I Define a single-particle basis f αg so that HF h^ α = "α α with the Hartree-Fock Hamiltonian defined as HF HF h^ = t^+u ^ext +u ^ HF I The term u^ is a single-particle potential to be determined by the HF algorithm. HF I The HF algorithm means to choose u^ in order to have HF hH^i = E = hΦ0jH^jΦ0i that is to find a local minimum with a Slater determinant Φ0 being the ansatz for the ground state. HF I The variational principle ensures that E ≥ E0, with E0 the exact ground state energy. Why Hartree-Fock? We will show that the Hartree-Fock Hamiltonian h^HF equals our definition of the operator f^ discussed in connection with the new definition of the normal-ordered Hamiltonian (see later lectures), that is we have, for a specific matrix element HF X hpjh^ jqi = hpjf^jqi = hpjt^+u ^extjqi + hpijV^jqiiAS ; i≤F meaning that HF X hpju^ jqi = hpijV^jqiiAS : i≤F The so-called Hartree-Fock potential u^HF brings an explicit medium dependence due to the summation over all single-particle states below the Fermi level F . It brings also in an explicit dependence on the two-body interaction (in nuclear physics we can also have complicated three- or higher-body forces). The two-body interaction, with its contribution from the other bystanding fermions, creates an effective mean field in which a given fermion moves, in addition to the external potential u^ext which confines the motion of the fermion. For systems like nuclei, there is no external confining potential. Nuclei are examples of self-bound systems, where the binding arises due to the intrinsic nature of the strong force. For nuclear systems thus, there would be no external one-body potential in the Hartree-Fock Hamiltonian. Definitions and notations Before we proceed we need some definitions. We will assume that the interacting part of the Hamiltonian can be approximated by a two-body interaction. This means that our Hamiltonian is written as the sum of some onebody part and a twobody part A A X X H^ = H^0 + H^I = h^0(xi ) + v^(rij ); (1) i=1 i<j with A X H0 = h^0(xi ): (2) i=1 The onebody part uext(xi ) is normally approximated by a harmonic oscillator or Woods-Saxon potential or for electronic systems the Coulomb interaction an electron feels from the nucleus. However, other potentials are fully possible, such as one derived from the self-consistent solution of the Hartree-Fock equations to be discussed here. Definitions and notations Our Hamiltonian is invariant under the permutation (interchange) of two particles. Since we deal with fermions however, the total wave function is antisymmetric. Let P^ be an operator which interchanges two particles. Due to the symmetries we have ascribed to our Hamiltonian, this operator commutes with the total Hamiltonian, [H^; P^] = 0; meaning that Ψλ(x1; x2;:::; xA) is an eigenfunction of P^ as well, that is P^ij Ψλ(x1; x2;:::; xi ;:::; xj ;:::; xA) = βΨλ(x1; x2;:::; xi ;:::; xj ;:::; xA); where β is the eigenvalue of P^. We have introduced the suffix ij in order to indicate that we permute particles i and j. The Pauli principle tells us that the total wave function for a system of fermions has to be antisymmetric, resulting in the eigenvalue β = −1. Definitions and notations In our case we assume that we can approximate the exact eigenfunction with a Slater determinant α(x1) α(x2) : : : : : : α(xA) β(x1) β(x2) : : : : : : β(xA) 1 Φ(x1; x2;:::; xA; α; β; : : : ; σ) = p ::::::::::::::: ; A! ::::::::::::::: σ(x1) σ(x2) : : : : : : σ(xA) (3) where xi stand for the coordinates and spin values of a particle i and α; β; : : : ; γ are quantum numbers needed to describe remaining quantum numbers. Definitions and notations The single-particle function α(xi ) are eigenfunctions of the onebody Hamiltonian hi , that is h^0(xi ) = t^(xi ) +u ^ext(xi ); with eigenvalues h^0(xi ) α(xi ) = t^(xi ) +u ^ext(xi ) α(xi ) = "α α(xi ): The energies "α are the so-called non-interacting single-particle energies, or unperturbed energies. The total energy is in this case the sum over all single-particle energies, if no two-body or more complicated many-body interactions are present. Definitions and notations Let us denote the ground state energy by E0. According to the variational principle we have Z ∗ E0 ≤ E[Φ] = Φ H^Φdτ where Φ is a trial function which we assume to be normalized Z Φ∗Φdτ = 1; where we have used the shorthand dτ = dx1dr2 ::: drA. Brief reminder on some linear algebra properties Before we proceed with a more compact representation of a Slater determinant, we would like to repeat some linear algebra properties which will be useful for our derivations of the energy as function of a Slater determinant, Hartree-Fock theory and later variational Monte Carlo. The inverse of a matrix is defined by A−1 · A = I A unitary matrix A is one whose inverse is its adjoint A−1 = Ay A real unitary matrix is called orthogonal and its inverse is equal to its transpose. A hermitian matrix is its own self-adjoint, that is A = Ay: Basic Matrix Features Matrix Properties Reminder Relations Name matrix elements T A = A symmetric aij = aji T −1 P P A = A real orthogonal k aik ajk = k aki akj = δij ∗ ∗ A = A real matrix aij = aij y ∗ A = A hermitian aij = aji y−1 P ∗ P ∗ A = A unitary k aik ajk = k aki akj = δij Basic Matrix Features Since we will deal with Fermions (identical and indistinguishable particles) we will form an ansatz for a given state in terms of so-called Slater determinants determined by a chosen basis of single-particle functions. For a given n × n matrix A we can write its determinant a11 a12 :::::: a1n a21 a22 :::::: a2n det(A) = jAj = ::::::::::::::: ; ::::::::::::::: an1 an2 :::::: ann in a more compact form as n! X pi jAj = (−1) P^i a11a22 ::: ann; i=1 where P^i is a permutation operator which permutes the column indices 1; 2; 3;:::; n and the sum runs over all n! permutations. The quantity pi represents the number of transpositions of column indices that are needed in order to bring a given permutation back to its initial ordering, in our case given by a11a22 ::: ann here. Basic Matrix Features, simple 2 × 2 determinant A simple 2 × 2 determinant illustrates this. We have a11 a12 0 1 det(A) = = (−1) a11a22 + (−1) a12a21; a21 a22 where in the last term we have interchanged the column indices 1 and 2. The natural ordering we have chosen is a11a22. Definitions and notations With the above we can rewrite our Slater determinant in a more compact form. In the Hartree-Fock method the trial function is the Slater determinant of Eq. (3) which can be rewritten as p 1 X P Φ(x1; x2;:::; xA; α; β; : : : ; ν) = p (−) P^ α(x1) β(x2) : : : ν(xA) = A!A^ΦH ; A! P where we have introduced the antisymmetrization operator A^ defined by the summation over all possible permutations of two particles. Definitions and notations It is defined as 1 X A^ = (−)pP^; (4) A! p with p standing for the number of permutations. We have introduced for later use the so-called Hartree-function, defined by the simple product of all possible single-particle functions ΦH (x1; x2;:::; xA; α; β; : : : ; ν) = α(x1) β(x2) : : : ν(xA): Definitions and notations Both H^0 and H^I are invariant under all possible permutations of any two particles and hence commute with A^ [H0; A^] = [HI ; A^] = 0: (5) Furthermore, A^ satisfies A^2 = A^; (6) since every permutation of the Slater determinant reproduces it. Definitions and notations The expectation value of H^0 Z Z ∗ ^ ∗ ^ ^ ^ Φ H0Φdτ = A! ΦH AH0AΦH dτ is readily reduced to Z Z ∗ ^ ∗ ^ ^ Φ H0Φdτ = A! ΦH H0AΦH dτ; where we have used Eqs. (5) and (6). The next step is to replace the antisymmetrization operator by its definition and to replace H^0 with the sum of one-body operators Z A Z ∗ ^ X X p ∗ ^ ^ Φ H0Φdτ = (−) ΦH h0PΦH dτ: i=1 p Definitions and notations The integral vanishes if two or more particles are permuted in only one of the Hartree-functions ΦH because the individual single-particle wave functions are orthogonal. We obtain then Z A Z ∗ ^ X ∗ ^ Φ H0Φdτ = ΦH h0ΦH dτ: i=1 Orthogonality of the single-particle functions allows us to further simplify the integral, and we arrive at the following expression for the expectation values of the sum of one-body Hamiltonians Z A Z ∗ ^ X ∗ ^ Φ H0Φdτ = µ(x)h0 µ(x)dx: (7) µ=1 Definitions and notations We introduce the following shorthand for the above integral Z ^ ∗ ^ hµjh0jµi = µ(x)h0 µ(x)dx; and rewrite Eq. (7) as Z A ∗ X Φ H^0Φdτ = hµjh^0jµi: (8) µ=1 Definitions and notations The expectation value of the two-body part of the Hamiltonian is obtained in a similar manner. We have Z Z ∗ ^ ∗ ^ ^ ^ Φ HI Φdτ = A! ΦH AHI AΦH dτ; which reduces to Z A Z ∗ ^ X X p ∗ ^ Φ HI Φdτ = (−) ΦH v^(rij )PΦH dτ; i≤j=1 p by following the same arguments as for the one-body Hamiltonian.
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