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# Chapter 7

The Hartree-Fock approximation
The Hartree method is useful as an introduction to the solution of many-particle system and to the concepts of self-consistency and of the self-consistent-ﬁeld, but its importance is conﬁned to the history of physics. In fact the Hartree method is not just approximate: it is wrong, by construction, since its wave function is not antisymmetric! A better approach, that correctly takes into account the antisymmetric character of the the wave functions is the HartreeFock approach. The price to pay is the presence in the equations of a non local, and thus more complex, exchange potential.

7.1

Hartree-Fock method

Let us re-consider the Hartree wave function. The simple product: ψ(1, 2, . . . , N ) = φ1 (1)φ2 (2) . . . φN (N ) (7.1)

does not satisfy the principle of indistinguishability, because it is not an eigenstate of permutation operators. It is however possible to build an antisymmetric solution by introducing the following Slater determinant: 1 ψ(1, . . . , N ) = √ N! φ1 (1) . . . φ1 (N ) . . . . . . φN (1) . . . φN (N )

(7.2)

The exchange of two particles is equivalent to the exchange of two columns, which induces, due to the known properties of determinants, a change of sign. Note that if two rows are equal, the determinant is zero: all φi ’s must be diﬀerent. This demonstrates Pauli’s exclusion principle. two (or more) identical fermions cannot occupy the same state. Note that the single-electron orbitals φi are assumed to be orthonormal: φ∗ (1)φj (1)dv1 = δij i (7.3)

52

(6. are identical).6) The integrals implicitly include summation over spin components. φ∗ (N ) N N φ1 (1) . .(6. φN (N ) dv1 . We follow the same path of Sec. .6) can then be written as ψ| ij gij |ψ = ij φ∗ (1)φ∗ (2)g12 [φi (1)φj (2) − δ(σi . .and two-electron operators: ψ| i fi |ψ = i φ∗ (1)f1 φi (1) dv1 i (7. . .13). φN (1) . the second term: φ∗ (1)φ∗ (2)g12 φj (1)φi (2) dv1 dv2 i j (7. The following property. Eq.2) used to derive Hartree equations. φ1 (N ) . dvN = φ∗ (1) . Since a determinant for N electrons has N ! terms. σj ) = 0 if σi = σj = 1 if σi = σj In summary: ψ|H|ψ = i φ∗ (1)f1 φi (1) dv1 i (7. φ∗ (N )F 1 N φ1 (1) .(7.7) is zero is i and j states are diﬀerent (the spin parts are not aﬀected by g12 and they are orthogonal if relative to diﬀerent spins). .where the “integral” on dv1 means as usual “integration on coordinates. From the above property it is immediate (and boring) to obtain the matrix elements for one. sum over spin components” . one gets N ! terms that. . φ1 (N ) . σj )φj (1)φi (2)] dv1 dv2 i j 53 . once integrated.9) + ij φ∗ (1)φ∗ (2)g12 [φi (1)φj (2) − δ(σi . φN (N ) dv1 . dvN (7. φ∗ (N ) 1 1 . is very useful: ψ|F |ψ = 1 N! φ∗ (1) . . If we assume that g12 depends only upon coordinates (as in Coulomb interaction) and not upon spin.8) where σi is the spin of electron i. . φN (1) .4) (by expanding the ﬁrst determinant. . . we need a way to write matrix elements between determinants on a ﬁnite paper surface. F φ∗ (1) . . and ψ| ij gij |ψ = ij φ∗ (1)φ∗ (2)g12 [φi (1)φj (2) − φj (1)φi (2)] dv1 dv2 i j (7. It is convenient to move to a scheme in which the spin variables are not explicitly included in the orbital index. valid for any (symmetric) operator F and determinantal functions ψ and ψ . and: δ(σi . σj )φj (1)φi (2)] dv1 dv2 i j (7.5) (as in the Hartree approximation). Eq.

1 Coulomb and exchange potentials Let us analyze the physical meaning of the Hartree-Fock equations. a (triangular) matrix ij of Lagrange multipliers would be needed. (7. Quantum theory of matter) that it is always possible to ﬁnd a transformation to a solution in which the matrix of Lagrange multipliers is diagonal.(7.g. due to the exchange term. 2. 7. σj )φk (2)φj (1)] dv2 = The energy of the system. in explicit form. 7. we can apply the variational principle.11) has normally an inﬁnite number of solutions. via the sum of eigenvectors of Eq. In principle we must impose normalization constraints such that not only all φi stay normalized (as we did in the derivation of Hartree’s equation) but also all pairs φi . can be expressed. on Slater’s book. The sum over index j runs only on occupied states. σj )φj (1)φk (2)] dv2 = j k φk (1) (7. there is an additional exchange term 3.11).10) or..(6. minus a term compensating the double counting of Coulomb repulsion and of theexchange energy: E= k k − <jk> φ∗ (1)φ∗ (2)g12 [φk (1)φj (2) − δ(σj . k j (7. i.Now that we have the expectation value of the energy. − h ¯2 2me 2 1 φk (1) 2 Zqe φk (1) + r1 2 qe [φj (2)φk (1) r12 − φ∗ (2) j j (7. the case j = k yields a nonzero contribution only if the spins are diﬀerent. the rest playing the role of excited states.11) k φk (1) − δ(σk . It can be shown however (details e. for electrons j with same spin as that of k. Eq.13): 1. of which only the lowestenergy N will be occupied by electrons.13) 54 .e. Let us carefully observe the diﬀerences with respect to Hartree equations.(7. Let us omit the details of the derivation and move to the ﬁnal Hartree-Fock equations: f1 φk (1) + j φ∗ (2)g12 [φk (1)φj (2) − δ(σk . Eqs. We assume that we re dealing with such a case.1. j also includes the case j = k. φj with same spin are orthogonal.12) Eq. analogously to the Hartree case. σk )φj (1)φk (2)] dv1 dv2 .9. We re-write them under the form − ¯2 h 2me 2 1 φk (1) − 2 Zqe ˆ φk (1) + VH (1)φk (1) + (Vx φk )(1) = r1 k φk (1).

2. j (7.084 Ry: a small quantity relative to the energy (∼ 1.5%). Vx (1.where we have introduced a ”Hartree potential” VH (it is not the same as in the Hartree equations!) and an ”exchange potential” Vx . because they require a more general form of the wave function. but not negligible.dvN . σj ) φ∗ (2) j 2 qe φk (2)φj (1) dv2 r12 (7. because the only physical quantity that it measures is our inability to ﬁnd the exact solution! 1 55 . This is in general not true.1 The origin of the name comes from the fact that the Hartree-Fock approximation misses part of the ”electron correlation”: the eﬀects of an electron on all others. .17) does not have the simple form of the Hartree potential: VH (1)φk (1).18) 7. This is the essence of the “conﬁguration interaction” (CI) method.16) δ(σk .. It has instead a form like ˆ (Vx φ)(1) ≡ typical of a non local interaction..15) We can verify that ρ(1) is equal to the probability to ﬁnd an electron in (1).2 Correlation energy The Hartree-Fock solution is not exact: it would be if the system under study were described by a wave function having the form of a Slater determinant.14) where we have introduce the charge density ρ(2) = j φ∗ (2)φj (2). The correlation energy in the case of He atom is about 0.. The energy diﬀerence between the exact and HartreeFock solution is known as correlation energy. This is present in HartreeFock via the exchange and electrostatic interactions. because electrons try to ”avoid” each other. Its practical application requires a sophisticated ”technology” to choose among the enormous Feynman called it stupidity energy. An obvious way to improve upon the Hartree-Fock results consists in allowing contributions from other Slater determinants to the wave function. (7. the probability P (r1 . N )|2 dv2 . ρ(1) = N The exchange term: ˆ (Vx φk )(1) = − j |Ψ(1. r2 ) to ﬁnd an electron at distance r1 and one as distance r2 from the origin is not simply equal to p(r1 )p(r2 ). that is. r12 (7. 2)φk (2)dv2 (7.1. where VH (1) comes from an integration over variable 2. For instance.. The Hartree potential is the same for all orbitals: VH (1) = j φ∗ (2) j 2 qe φj (2)dv2 ≡ r12 ρ(2) 2 qe dv2 . more subtle eﬀects are not accounted for.

20) In the ground state. and to classify the solution with the ”traditional” quantum numbers n. Such technique. less heavy methods (the socalled Møller-Plesset. much used in condensed-matter physics. A completely diﬀerent approach. the two electrons have opposite spin (δ(σ1 . m. σ2 )φ1 (2)φ2 (1)] dv2 = r12 (7. N/2 (7.(7.3 The Helium atom The solution of Hartree-Fock equations in atoms also commonly uses the central ﬁeld approximation. for each k there is a spin-up and a spin-down orbital. formed by a same function of r. σ2 )φ1 (2)φ2 (1)] dv2 = 1 φ1 (1). no total spin – in the following form: Fφk = k φk . which produces equations that are reminiscent of Hartree-Fock equations. one speaks of Restricted Hartree-Fock (RHF) for the frequent case in which all orbitals are present in pairs.19). . It is of 56 .20). Eq. for the ground state is the same as the Hartree equation. . . − h ¯2 2me 2 1 φ1 (1) 2 Zqe q2 φ1 (1) + φ∗ (2) e [φ2 (2)φ1 (1) 2 r1 r12 −δ(σ1 . − (7. This means that the Hartree-Fock equation.number of possible Slater determinants a subset of most signiﬁcant ones. the two electrons have opposite spin and there is thus no exchange.11). In the following. σ2 ) = 0) and occupy the same spherically symmetric orbital (that is: φ1 and φ2 are the same function. Eq. k = 1. In general. Let us re-write the Hartree-Fock equation – for the restricted case. This allows to factorize Eqs. .(7. is Density-Functional Theory (DFT). MP.e. is used in quantum chemistry to get high-precision results in small molecules. i. approaches) rely on perturbation theory to yield a rather good estimate of correlation energy.2 Code: helium hf gauss The radial solution of Hartree-Fock equations is possible only for atoms or in some model systems. .(6. Other.21) The index k labels the coordinate parts of the orbitals. in analogy with the variational method. φ). this will always be the case.(7. 7. Eq.19) Since the integrand in the ﬁrst integral is zero. In fact.11) into a radial and an angular part. 7. In most cases the solution is found by expanding on a suitable basis set. multiplied by spin functions of opposite spin. the Hartree-Fock equations. computationally very heavy. F is called the Fock operator. reduce to − h ¯2 2me + 2 1 φ1 (1) − 2 Zqe φ1 (1) + r1 φ∗ (2) 1 2 qe [φ1 (2)φ1 (1) − φ1 (2)φ1 (1)] dv2 r12 1 φ1 (1) φ∗ (2) 2 2 qe [φ2 (2)φ1 (1) − δ(σ1 .1. For He.

2 (7.(7. (7.22) is more complex than a normal secular problem solvable by diagonalization.(7. .c 57 .24) is called density matrix.uniud.f902 (or helium hf gauss. i gijlm = b∗ (r1 )bj (r1 )g12 b∗ (r2 )bm (r2 )dr1 dr2 .25) the sum over states between parentheses in Eq. The basic ingredients are the same as in code hydrogen gauss (for the calculation of single-electron matrix elements and for matrix diagonalization) and helium gauss (for matrix elements of Coulomb repulsion between electrons).e. 2 3 http://www. depends upon its own eigenvectors. . with no special trick or algorithm. Eq.22) where c(k) = (c1 . i. a generalized diagonalization is performed at each step).it/%7Egiannozz/Corsi/MQ/Software/F90/helium hf gauss. We ﬁnd the Rothaan-Hartree-Fock equations: F c(k) = (k) (k) (k) (k) k Sc (7. using a basis set of S Gaussians.it/%7Egiannozz/Corsi/MQ/Software/C/helium hf gauss.23) that after some algebra can be written as  N/2 k=1  (k)∗ cl c(k)  m Fij = fij + l m 2 1 gijlm − giljm . Sij = bi |bj .ﬁsica.course a non-local operator which depends upon the orbitals φk .uniud. 7. the Fock matrix is re-calculated using the density matrix at the preceding step.c3 ) solves Hartree-Fock equations for the ground state of He atom. The problem of Eq. then the same set of Gaussians with rescaled coeﬃcients. in which at each step a ﬁxed matrix is diagonalized (or. S is the superposition matrix. Code helium hf gauss.2.6875 (see Sect. since the Fock matrix. Let us look now for a solution under the form of an expansion on a basis of functions: (k) φk (r) = i ci bi (r). C. until energy converges within a given numerical threshold. It is however possible to reconduct the solution to a selfconsistent procedure.f90 http://www. You may take the energy given by helium hf radial as the reference. for a non-orthonormal basis.24) where. F is the matrix of the Fock operator on the basis set functions: Fij = bi |F|bj .1 Laboratory • Observe how the ground-state energy changes as a function of the number of Gaussians and of their coeﬃcients. .2). The self-consistent procedure is even simpler than in code helium hf radial: at each step.ﬁsica.24). i l (7. The two terms in the second parentheses come respectively from the Hartree and the exchange potentials.(7. Start with the 3 or 4 Gaussian basis set used for Hydrogen. . such that they ﬁt a Slater 1s orbital for He+ (Z = 2) and for a Hydrogen-like atom with Z = 1. cN ) is the vector of the expansion coeﬃcients. c2 . with the notations introduced in this chapter: fij = b∗ (r1 )f1 bj (r1 )dr1 .

. with coeﬃcients: α1 = 0. and – the 1s orbital from code helium hf radial. Compare it with – the 1s Slater orbital for Z = 1. α2 = 1. Z = 2.u. 58 .6875. plot it. α4 = 38.297104. Z = 1.216677 a.236745. α3 = 5.749982.• Write to ﬁle the 1s orbital (borrow the relative code from hydrogen gauss). Beware: there is a factor between the orbitals calculated with radial integration and with a Gaussian basis set: which factor and why? • Try the following optimized basis set with four Gaussians.

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