1. Quantum Springs

2. Harmonic Oscillator Our next model is the quantum mechanics version of a spring: Serves as a good model of a vibrating (diatomic) molecule The simplest model is a harmonic oscillator:

3. Harmonic Oscillator What does this potential mean? Let’s take a look at a plot: x = spring stretch distance V x 0 = “equilibrium bond length”

4. Harmonic oscillator Let’s do the usual set up: The Schrodinger equation: Insert the operators Rearrange a little This is a linear second order homogeneous diff. eq., BUT with non-constant coefficients… Too hard to solve by hand, so we’ll do it numerically on the computer!

5. Numerov technique Just as a matter of note, we have to use rescaled x, , and E for the numerical solution algorithm we’ll use: the Numerov technique. Get spit out of the Numerov alg. Scaling coefficients

6. Numerov technique  is the “reduced mass”: k is the “spring constant” Measures “stiffness” of the bond m1m1 m2m2 With the spring constant and reduced mass we can obtain fundamental vibrational frequencies

7. Solve the Harmonic Oscillator

8. E v = 0

9. Solve the Harmonic Oscillator E v = 1 E v = 0

10. Solve the Harmonic Oscillator E v = 2 E v = 1 E v = 0

11. Solve the Harmonic Oscillator E v = 3 E v = 2 E v = 1 E v = 0

12. Solve the Harmonic Oscillator E v = 4 E v = 3 E v = 2 E v = 1 E v = 0

13. Solve the Harmonic Oscillator E v = 5  E = ħ  E v = 4 E v = 3 E v = 2 E v = 1 E v = 0 v = {0, 1, 2, 3, …}

14. Solve the Harmonic Oscillator Ground State

15. Solve the Harmonic Oscillator First Excited State

16. Solve the Harmonic Oscillator Second Excited State

17. Solve the Harmonic Oscillator Third Excited State

18. Solve the Harmonic Oscillator Fourth Excited State

19. Solve the Harmonic Oscillator Fifth Excited State # nodes, harmonic oscillator = v

20. Anharmonic Oscillator Real bonds break if they are stretched enough. Harmonic oscillator does not account for this! A more realistic potential should look like: Energetic asymptote

21. Anharmonic Oscillator Unfortunately the exact equation for anharmonic V(x) contains an infinite number of terms We will use a close approximation which has a closed form: the Morse potential

22. Anharmonic Oscillator Wave function dies off quickly when it gets past the potential walls Ground State # nodes, anharmonic oscillator = v

23. Anharmonic Oscillator First Excited State Note how anharmonic wave functions are asymmetric

24. Anharmonic Oscillator A energy increases toward the asymptote, eigenvalues of the anharmonic oscillator get closer and closer Energetic asymptote

25. Anharmonic Oscillator Bond almost broken…

26. Anharmonic Oscillator Energetic asymptote Bond breaks! D 0 = bond energy