10.
675 LECTURE 3
RICK RAJTER
1. Today Hartree Theory and Self Consistent Solutions Slater Determinant HartreeFock Theory Reminder, Tuesdays Evening Class 78:30 rm 1115 2. Concepts Mean Field Theory Self Consistent Solutions 3. Quick Review H0 = Ei 0 for the ground state system. The full hamiltonian is below. H= 1 1 2 Zk ecri Rk + i 2 i v r rj i j i i<j i
N N M N N
The diculty arises in the last term, because its not separable. 4. Hartree Theory 1928 Trial Wave Function 1 (x1 )2 (x2 )
Go from a many bodied problem to a single electron problem.
j electron density of j.
j () = ( j ()
r j r) r Sooo... N N N 1 (x1 )2 (x2 ) 1 r rj |ri rj | i i<j i j=2 and that is the Mean Field Term.
Hartree H1 =
(ri ) 1 2
Zk + dri i 2 i |r rj | j=2 i i j ri R k
Hartree Hartree Hartree ... + HN + H2 Summed up from H1 for each electron. Har Har Har Thus, we solve H1 1 (1) = 1 1 (1) Example
Date: Fall 2004.
1
RICK RAJTER
Initially 1 (1)2 (2)3 (3) 1 (1)2 (2)3 (3) 1 (1)2 (2)3 (3) 1 (1)2 (2)3 (3) 1 (1)2 (2)3 (3) 1 (1)2 (2)3 (3) Convergence! The major problem left to deal with is the fact that 1 (x1 )2 (x2 ) is symmetric in regards to exchange of electron positions. Thus, we need to make it antisymmetric by converting via a slater determinant. 5. Slater Determinant 1 (x1 , x2 ) = [i (x1 )i (x2 ) i (x2 )i (x1 )] 2 1 (x ) i (x2 ) = i 1 j (x1 ) j (x2 ) 2 The above is known as a Slater determinant.
Now, we want to expand this relationship for an i (1) i (2) 1 . (x1 x2 x3 ...xN ) = N . . i (N ) with each spin being orthonormal! i ( i = ij x) xdx 6. Hartree + Slater Determinant H o = Eo Reorganizing via multiplying each side by Eo = H Hf o dx1 dx2 o
Hf
Nelectron system.
j (1) k (1) j (2) k (2) . . . . . . j (N ) k (N )
10.675 LECTURE 3
H Hf = where
1 r1 r2
1 1 2 Zk i + k 2 r1 r2 ri R
k 1 r12
is often written Eo = 1 2
N a
dx1 (x1 )[ a
1 2 Zk ] (x ) a 1 2 i ri R k
k
N N
dx1 dx2 (1) (2) a b
1 a (1)b (2) r12
N N 1 1 dx1 dx2 (1) (2) a a (2)b (1) + b 2 r12 Term 1 is the energy of a single electron. Term 2 is the coulomb interaction between electron 1 and 2. Term 3 is the exchange energy term. The exchange energy term is a result of using the slater determinant, which deals with the exchange of electrons. This is a correction to the mean eld term. To note, when a=b, the last terms cancel out.
7. Symbolic Notation The above was a complete mess, to simplify well use the following notation. Zk The single electron term h(1) = 1 2 r1k 2 1 1 The coloumb term: Jb (1)a (1) = [ x2 (2)r12 b (2)]a (1) d b 1 The exchange term: Kb (1)a (1) = [ dx2 b (2)r12 a (2)]b (1) Condense further to symbolic notation. 1 Eo = a < a|h|a > + 2 ab < ab||ab > And this is equivalent to the entire mess is the previous section. Lets expand the last just to be clear. term 1 < ab||ab >= 1 ab [aa|bb] [ab|ba] ab 2 2 In usage, this would appear as [h(1) + b=a Jb (1) Kb (1)]a (1) = a a (1) and the term in brackets is called the fock operator. 8. Basis Sets
2 |1 ()|2 dri = 1 (r1 )dr1 which is probability of nding electrons. r 1 (r1 )dr1 = 1 over all space. A basis set is a set of functions introduced to t s, but its not a rigorous basis set as solved analytically. () = a ca ua (r) r where ca is a complex number and ua (r) is the basis. Together, they form vectors. du ( b () = ab when orthnormal r r)u r a ca = drUa ()() r r
9. Dirac Notation =< a |b >=< a|b > where : < a| is called the bra and |b > is called the ket
H is a linear operator.
H(Ca |a > +Cb |b >) = Ca H |a > +Cb H |b >
( a () a r) r
RICK RAJTER
H dr =< a|H|b > a b H is hermitian meaning H = H < a|H |b >=< b|Ha > < a|Hb >=< Ha|b > < a|b > a is the complex conjugate. The bras, kets dene a matrix Hab H11 =< a|H|b >= H21 ... H12 H22 ... ... ... ...
10. Hermitian Details Important properties Eigenfunctions are orthonormal Eigenvalues are real All observables are eigenvalues of hermitian operators dp() = | < U | > |2 d = probability of getting . dp() = | < | > |2 r r
