HARTREE METHOD

Many-Body Problems
Course Title:
Advance Quantum Mechanics(502)
Presents By:
Danish Raza,PH-01,M.S (Physics)
Submitted To:
Dr. Tanweer Iqbal
Assistant Professor,Department of Physics
NEDUET
Hartree Method:
Contents:

Introduction about Hartree Method

 Hartree Approximation for helium atom with
unperturbation case
Hartree Approximation for helium atom with
perturbation case using variational method
Hartree Method:
• Introduction to Hartree Method:
• In Quantum Mechanics,Hartree method is used to solve the
many-body problems.
• Many-Body-Problem ;like helium or hydrogen molecule which
contains three or more electron’s interaction among them.
• It is a single electron approximation technique in which the
Hamiltonian for many body problem is split up into individual
single electron Hamiltonians.
H = H(r1) + H(r2) + H(r3) ................H(rN).
 Hartree Method:
• Each electron has its unique wave function. The complete
wave function for N-electron system( Hartree function) ψh is
represented as the product of wave functions of different
electronic motion.
ψh(r1,r2,...,rN) = φ1 (r1).φ2(r2).................φN(rN).
• In this method , electronic mass me , electron charge e,
reduced Planck’s constant ħ and Coulomb force constant k are
assumed to be 1.
e = me = ħ = k = 1
Hartree Method:
• Stationary state wave functions are obtained by solving
Schrodinger Time-Independent Wave Equation for each
electron.
h(ri)φ(ri) = Ei φ(ri)
Where h(ri) = Hilmatonian for i-th electron
• φ(ri) and Ei is the eigan function and eigan energy for i-th
electron,are called orbital and orbital energy.
He atom as an example:

r12=|r1−r2|
Hartree Method:
Hartree Approximation With Unperturbation Case:
• In these problems it is assumed that Coloumb potential
(electron-electron repulsion) does not affect the motion of
each electron. It means that coloumb potential neglected.
• In the absence of coloumb potential the Himaltonian will be

• He atom wave function as a product of the individual electron

wave functions (here approximated as hydrogen-like wave
functions)
Hartree Method:
• As we know the wave function and energy of hydrogen atom
are

Hydrogen Wave Radial Wave Angular Wave Energy of Hydrogen atom

Function Function Function

• n=1, l=m=0 for hydrogen atom

• n:Principal quantum number connected with total energy
• ℓ: Orbital angular momentum quantum number connected
with magnitude of angular momentum
• m: Magnetic quantum number connected with z-component
of angular momentum vector
Hartree Method:
• After solving Schrodinger Time-Independent Wave Equation
and Using hydrogen wave function and energy,the wave
function and energy for He atom will be

• The actual ground state energy for helium is -78 eV.This is due
to the neglecting coloumb potential(unperturbed potential).
 Hartree Method:
Hartree Approximation with Perturbation:
• The coloumb potential acts a small perturbation so we use
variational method to find the expectation value of the
potential.
• the expectation value of the coloumb potential found by as

• Hartree assumed that each electron moves in the

averaged position under the electrostatic repulsion of
surrounding electrons(Self-Consistent Method) this
averaged potential as an effective potential Veff.
• The Himaltonian for each electron will be:
Hartree Method:
• Substituting the himaltonian in expectation energy expression
we will get,the effective potential by as

• The effective potential depends upon wave function of

elctrons,So first we find the effective potential assuming a
guess function by iterative method(computer based program).
• For Best guess function this method gives ground state energy
is -74 eV,which has nearly 5% error as compared to exact
value of helium.
• This error is due to ignoring electronic spin that was modified
by Fock.Then it was called Hartree-Fock Method.
Hartree Fock Method:
Slater Determinant
• Each electron has same energy if r1 and r2 were
interchanged(exchange degeneracy),this problem was solved
by introducing Slater Determinant.
• As we know that Hamiltonian operator is commutative i.e
does not change by exchanging the coordinates of two
electrons:

• Schrodinger Equation
• To revert the wave function,introduce exchange operator P12

• This indicates that the Hamiltonian and exchange operators

have simultaneous eigenstates. Moreover, (P12)2 =1
Hartree Fock Method:
• Therefore,the symmetric and antisymmetric wave function
corresponding to 1 eigen values

• According to Pauli’s Exclusion Principle,No two electron have

same spin,i.e wave functions must be antisymmetric.

• This is called Slater determinant.

Hartree Fock Method:
Applications:
• The Hartree–Fock method has its typical application
in the solution of the Schrödinger equation for atoms,
molecules, nanostructures and solids but it has also
found widespread use in nuclear physics.
References:
 Chapter No.2,Density function Theory in Quantum Chemistry,
Tsuenda,T,2014,Springer
 https:www1.udel.edu/pchem/C444/spLectures/04222008b.pdf
Helium Atom, Approximate Methods 22nd April 2008
• https://en.wikipedia.org/wiki/Hartree–Fock_method
• https://www.slideshare.net/premashiskumar/the-hartree-fock-
method
• https://www.slideshare.net/MasumaAkhatar/helium-front

Thanks!