Schrödinger Representation – Schrödinger Equation Time dependent Schrödinger Equation Developed through analogy to Maxwell’s equations and knowledge of the Bohr model of the H atom. Hamiltonian kinetic potential energy energy Sum of kinetic energy and potential energy. The potential, V, makes one problem different form another H atom, harmonic oscillator. Q.M. one dimension three dimensions recall Copyright – Michael D. Fayer, 2017 1 1 1

Getting the Time Independent Schrödinger Equation wavefunction If the energy is independent of time Try solution product of spatial function and time function Then independent of t independent of x, y, z divide through by Copyright – Michael D. Fayer, 2017 2 2 2

Can only be true for any x, y, z, t if both sides equal a constant. depends only on t depends only on x, y, z Can only be true for any x, y, z, t if both sides equal a constant. Changing t on the left doesn’t change the value on the right. Changing x, y, z on right doesn’t change value on left. Equal constant Copyright – Michael D. Fayer, 2017 3 3 3

Both sides equal a constant, E. Energy eigenvalue problem – time independent Schrödinger Equation H is energy operator. Operate on f get f back times a number. f’s are energy eigenkets; eigenfunctions; wavefunctions. E Energy Eigenvalues Observable values of energy Copyright – Michael D. Fayer, 2017 4 4 4

Time Dependent Equation (H time independent) Integrate both sides Take initial condition at t = 0, F = 1, then C = 0. Time dependent part of wavefunction for time independent Hamiltonian. Time dependent phase factor used in wave packet problem. Copyright – Michael D. Fayer, 2017 5 5 5

Total wavefunction for time independent Hamiltonian. E – energy (observable) that labels state. Normalization Total wavefunction is normalized if time independent part is normalized. Expectation value of time independent operator S. S does not depend on t, can be brought to other side of S. Expectation value is time independent and depends only on the time independent part of the wavefunction. Copyright – Michael D. Fayer, 2017 6 6 6

Expectation value of operator representing observable for state Equation of motion of the Expectation Value in the Schrödinger Representation Expectation value of operator representing observable for state example - momentum In Schrödinger representation, operators don’t change in time. Time dependence contained in wavefunction. Want Q.M. equivalent of time derivative of a classical dynamical variable. P P classical momentum goes over to momentum operator want Q.M. operator equivalent of time derivative Definition: The time derivative of the operator , i. e., is defined to mean an operator whose expectation in any state is the time derivative of the expectation of the operator . Copyright – Michael D. Fayer, 2017 7 7 7

time dependent Schrödinger equation. Want to find Use time dependent Schrödinger equation. product rule time independent – derivative is zero Use the complex conjugate of the Schrödinger equation . (operate to left) Then , and from the Schrödinger equation From complex conjugate of Schrödinger eq. From Schrödinger eq. Copyright – Michael D. Fayer, 2017 8 8 8

This is the commutator of H A. Therefore This is the commutator of H A. The operator representing the time derivative of an observable is times the commutator of H with the observable. Copyright – Michael D. Fayer, 2017 9 9 9

Solving the time independent Schrödinger equation The free particle momentum problem Free particle Hamiltonian – no potential – V = 0. Commutator of H with P commute Simultaneous Eigenfunctions. Copyright – Michael D. Fayer, 2017 10 10 10

Free particle energy eigenvalue problem Use momentum eigenkets. energy eigenvalues Therefore, Energy same as classical result. Copyright – Michael D. Fayer, 2017 11 11 11

Particle in a One Dimensional Box Infinitely high, thick, impenetrable walls Particle inside box. Can’t get out because of impenetrable walls. Classically E is continuous. E can be zero. One D racquet ball court. Q.M. E can’t be zero. Schrödinger Equation Energy eigenvalue problem Copyright – Michael D. Fayer, 2017 12 12 12

1. The wave function must be finite everywhere. For Want to solve differential Equation, but solution must by physically acceptable. Born Condition on Wavefunction to make physically meaningful. 1. The wave function must be finite everywhere. 2. The wave function must be single valued. 3. The wave function must be continuous. 4. First derivative of wave function must be continuous. Copyright – Michael D. Fayer, 2017 13 13 13

Functions with this property sin and cos. Second derivative of a function equals a negative constant times the same function. Functions with this property sin and cos. These are solutions provided Copyright – Michael D. Fayer, 2017 14 14 14

Solutions with any value of a don’t obey Born conditions. j = x Well is infinitely deep. Particle has zero probability of being found outside the box.  = 0 for Function as drawn discontinuous at To be an acceptable wavefunction Copyright – Michael D. Fayer, 2017 15 15 15

–b b n is an integer Integral number of half wavelengths in box. Zero at walls. b –b Have two conditions for a2. Solve for E. Energy eigenvalues – energy levels, not continuous. L = 2b – length of box. Copyright – Michael D. Fayer, 2017 16 16 16

Energy levels are quantized. Lowest energy not zero. L = 2b – length of box. wavefunctions including normalization constants First few wavefunctions. Quantization forced by Born conditions (boundary conditions) Fourth Born condition not met – first derivative not continuous. Physically unrealistic problem because the potential is discontinuous. Like classical string – has “fundamental” and harmonics. Copyright – Michael D. Fayer, 2017 17 17 17

Particle in a Box Simple model of molecular energy levels. Anthracene L p electrons – consider “free” in box of length L. Ignore all coulomb interactions. E2 E1 S0 S1 DE Calculate wavelength of absorption of light. Form particle in box energy level formula Copyright – Michael D. Fayer, 2017 18 18 18

Big molecules absorb in red. Small molecules absorb in UV. Anthracene particularly good agreement. Other molecules, naphthalene, benzene, agreement much worse. Important point Confine a particle with “size” of electron to box size of a molecule Get energy level separation, light absorption, in visible and UV. Molecular structure, realistic potential give accurate calculation, but it is the mass and size alone that set scale. Big molecules absorb in red. Small molecules absorb in UV. Copyright – Michael D. Fayer, 2017 19 19 19

Particle in a Finite Box – Tunneling and Ionization Box with finite walls. Time independent Schrödinger Eq. Inside Box V = 0 Second derivative of function equals negative constant times same function. Solutions – sin and cos. Copyright – Michael D. Fayer, 2017 20 20 20

Two cases: Bound states, E < V Unbound states, E > V Solutions inside box or Outside Box Two cases: Bound states, E < V Unbound states, E > V Bound States Second derivative of function equals positive constant times same function. Not oscillatory. Copyright – Michael D. Fayer, 2017 21 21 21

Then, solutions outside the box Try solutions Second derivative of function equals positive constant times same function. Then, solutions outside the box Solutions must obey Born Conditions can’t blow up as Therefore, Outside box exp. decays Inside box oscillatory Copyright – Michael D. Fayer, 2017 22 22 22

b = x j Outside box exp. decays Inside box oscillatory The wavefunction and its first derivative continuous at walls – Born Conditions. x probability 0 Expanded view For a finite distance into the material finite probability of finding particle. Classically forbidden region V > E. b x j = Copyright – Michael D. Fayer, 2017 23 23 23

Tunneling - Qualitative Discussion j = X Classically forbidden region. Wavefunction not zero at far side of wall. Probability of finding particle finite outside box. A particle placed inside of box with not enough energy to go over the wall can Tunnel Through the Wall. Formula derived in book mass = me E = 1000 cm-1 V = 2000 cm-1 Wall thickness (d) 1 Å 10 Å 100 Å probability ratio 0.68 0.02 3  10-17 Ratio probs - outside vs. inside edges of wall. Copyright – Michael D. Fayer, 2017 24 24 24

e-l V Chemical Reaction not enough energy to go over barrier Temperature dependence of some chemical reactions shows to much product at low T. V > kT . V Decay of probability in classically forbidden region for parabolic potential. e-l tunneling distance mass barrier height parameter light particles tunnel Copyright – Michael D. Fayer, 2017 25 25 25

H C H H Methyl Rotation Methyl groups rotate even at very low T. Radioactive Decay repulsive Coulomb interaction nuclear attraction strong interaction some probability outside nucleus Copyright – Michael D. Fayer, 2017 26 26 26

E large enough - ionization Unbound States and Ionization -b b bound states V(x) = V If E > V - unbound states E large enough - ionization E < V Inside the box (between -b and b) V = 0 Solutions oscillatory Outside the box (x > |b|) E > V Solutions oscillatory Copyright – Michael D. Fayer, 2017 27 27 27

Wavefunction has equal amplitude everywhere. unbound state In limit Wavefunction has equal amplitude everywhere. To solve (numerically) Wavefunction and first derivative equal at walls, for example at x = b Copyright – Michael D. Fayer, 2017 28 28 28

Continuous range of energies - free particle For E >> V for all x As if there is no wall. Continuous range of energies - free particle Particle has been ionized. Free particle wavefunction Copyright – Michael D. Fayer, 2017 29 29 29

Tunneling Ionization In real world potential barriers are finite. 30 Copyright – Michael D. Fayer, 2017 30 30 30