Rick Rajter: N N M K 2 I N N

10.
675 LECTURE 2
RICK RAJTER
1. Last Lecture Review Many Body PE surface. Schrdingers Equation (SE) o # Dimensions 2. Important Concepts Many Body PE surface. Schrodingers Equation. # Dimensions 3. Many Body SE 1 2
Zk 1 + i 2 i r vecrj i i<j i i j ri R k
N N M N N
H=
3N 6 Degrees of Freedom (DOF) in NonLinear Case 3N 5 DOF for linear. Each Molecule moves in the directions, hence 3N. In nonlinear, substract 3 rotation and 3 translation (6). In linear, substract 3 translation and 2 rotation (5). 4. Today QM and Atomic Orbitals Permutation Pi j and Pauli Principle Spin Orbitals Valence band theory and molecular 5. Born Oppenheimer approximation Theory that the electrons relax far faster than the protons. Thus, we can decouple nuclearnuclear interaction terms from the electron terms.
Date: Fall 2004.
1
RICK RAJTER
6. Hydrogen Atom Hi (r) = Ei i (r) H Hamiltonian i Atomic orbital r position vector We can solve for the hydrogen wave function explicitly nlm () = Rnl Ylm (, ) r NOTE: the solution neglects or doesnt include the eects of spin. 7. Spin
1 Electrons have an intrinsic spin +/ 2 or . This spin is a consequence of the SE in its relativistic formulation, i.e. the Dirac equation. Thus, degeneracy of the
atomic orbitals exists.
x r Let be the spin coordinate.
= (, ). = Total wave functions of the many body N electron system = (x1 , x2 , x3 ...xN )
8. Pauli Principle must be anti symmetric with respect to exchange. Pi j Permutation operator, which exchanges electron i with j. P12 (x1 , x2 , x3 ) = (x2 , x1 , x3 ) = (x1 , x2 , x3 ) 9. Helium Atom Introduce spin orbital concept ( where = ( ) x x) r, The ground state wave function is the lowest state. 0 = ( 1 ) ( 2 ) which is our trial wavefunction. x x 10. Slater Determinant x x 0 = ( 1 ) ( 2 ) Not antisymmetric, so its a poor trial wave function. Try this instead. 1 x x x x 0 = 2 ( ( 1 ) ( 2 ) ( 2 ) ( 1 )) Which is antisymmetric AND coupled. A more convenient format is a slater determinant. 1 ( 1 ) ( 2 ) x x = x x 2 ( 1 ) ( 2 ) 11. Spatial Functions (r1 )(r2 ) abbreviate as (1)(2)
Spin Function or .
(1)(2) and (1)(2) are symmetric
(1)(2) and (1)(2) violates indistinguishability. Implies we have an
independent measure of spins.
10.675 LECTURE 2
12. Combined Spin and Spatial Functions Now that we have the electronic and spatial wave functions, we combine to get a complete trial wave function for helium. 1 (1 2 ) = (1)(2) [(1)(2) (1)(2)] 2 Notethat (1)(1)dr = (2)(2)dr = 1 from the overlap integral S = a b d() r 13. Hydrogen Gas Valence bond theory, so valence bond wave function.
Choose a trial wave function (Heiter and London).
= a (1)b (2) or b (1)a (2)
So, we need to create an overall antisymmetric wave function of both electronic
and spatial wave functions.
= 1 1 x x x x [a (1)b (2) + b (1)a (2)] ( ( 1 ) ( 2 ) ( 2 ) ( 1 )) 2 2 2 + 2S
which is overall antisymmetric (both spatially and electronically). 14. Hydrogen Hamiltonian The complete Hamiltonian is as follows. H= 1 2 1 2 1 1 1 1 1 + a b r 1 r2 2 1 2 2 r1 R a r2 R r1 Rb r2 R
Where denotes electron position vector, R denotes nucleus position vector. r 15. Perturbation Theory Summary on pg 68 of S&O Dissociation Energy H2 System Calculated De = 3.15 eV Re=0.87A Experimental De = 4.75 Re = 0.741 A Major approximations Form of the trial wavefunction BO approximation Perturbation Theory (how we solve it) 16. Molecular Orbital Approach Trial Wave Function 1 1 = [(a + b )(1)(a + b )(2)] ((1)(2) (1)(2)) 2 2 + 2S 2 The spatial orbital section is symmetric, and the electronic orbitals are antisymmetric. A symmetric function times a antisymmetric function leads to an overall anti symmetric function. This is essentially a linear combination of spatial orbitals (1) and (2).
RICK RAJTER
If we multiply out the spatial terms, we get the following. a (1)a (2) + b (1)b (2) + a (1)a (2) + b (1)a (2) The rst two terms are ionic because both electrons are centered on 1 atom. The 2nd two terms are covalent, as the electrons are shared. Unfortunately, if we maintain this balance, this implies that ioniccovalent characteristics should occur 50/50. This is obviously not the case. Thus, a fudge factor can be used to reduce the ionic content of the wave function. Then we can solve variationally. Typically, is set to 0.26.

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