atoms and light. Chapter Goal: To understand the structure and properties of atoms.

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1 Quantum mechanics provides us with an understanding of atomic structure and atomic properties. Lasers are one of the most important applications of the quantummechanical properties of atoms and light. Chapter Goal: To understand the structure and properties of atoms.

2 Topics today: Two dimensional waves The Hydrogen Atom: Angular Momentum and Energy The Hydrogen Atom: Wave Functions and Probabilities The rest on Wednesday

3 D. Eigler (IBM) 48 Iron atoms assembled into a circular ring. The ripples inside the ring reflect the electron quantum states of a circular ring (interference effects).

4 Particle in box: 2 dimensions Motion in x direction Motion in y direction For a rectangular box, the x and y motions are independent. For a general box, the classical motion may be chaotic.

5 Particle in box: 2 dimensions Schrodinger s equation: Solution is a product of standing wave solutions, one for each dimension: The energy is the sum of energies along each dimension:

6 Quantum Wave Functions for 2-D box Probability (2D) Ground state: same wavelength (longest) in both x and y Need two quantum # s, one for x-motion one for y-motion Denote a q# pair (n x, n y ) Ground state: (1,1) Wavefunction Probability = (Wavefunction) 2 One-dimensional (1D) case

7 2D excited states (n x, n y ) = (2,1) (n x, n y ) = (1,2) These have exactly the same energy for a square box, but the probabilities look different. The different states correspond to ball bouncing in x or in y direction.

8 Particle in a box What quantum state could this be? A. n x =2, n y =2 B. n x =3, n y =2 C. n x =1, n y =2

9 Waves confined by a circular box vanish at the edge radius and are products of a radial wave and an azimuthal wave: The two quantum numbers n and m count nodes in the radial and azimuthal probability densities.

10 Three dimensions Object can have different velocity (hence wavelength) in x, y, or z directions. Need three quantum numbers to label state (n x, n y, n z ) labels each quantum state (a triplet of integers) Each point in three-dimensional space has a probability associated with it. Not enough dimensions to plot probability But can plot a surface of constant probability.

11 Particle in 3D box Ground state surface of constant probability (n x, n y, n z )=(1,1,1) 2D case

12 (121) (211) (112) All these states have the same energy, but different probabilities

13 (222) (221)

14 3-D particle in box: summary Three quantum numbers (n x,n y,n z ) label each state n x,y,z =1, 2, 3 (integers starting at 1) Each state has different motion in x, y, z Quantum numbers determine Momentum in each direction: e.g. p x = h h = n x λ nx 2L Energy: for a cube E = p 2 x 2m + p 2 y 2m + Some quantum states have same energy for a cube. The degeneracy is related to the symmetry of the cube. p 2 z 2m = E o ( n 2 x + n 2 2 y + n ) z

15 Use spherical coordinates matched to symmetry Must write the Laplacian in spherical coordinates and solve. Solutions are products of waves in each coordinate Solutions specified by three quantum numbers n, l, m with

16 Use spherical coordinates matched to symmetry Solutions are products of waves in each coordinate Solutions specified by three quantum numbers n, l, m with

17 Solutions to the Schrödinger equation for the hydrogen atom potential energy exist only if three conditions are satisfied: 1. The atom s energy must be one of the values where a B is the Bohr radius. The integer n is called the principal quantum number. These energies are the same as those in the Bohr hydrogen atom. Note that the energy does not depend on l and m. Thi is a quirk of the Coulomb potential.

18 2. The angular momentum L of the electron s orbit must be one of the values The integer l is called the orbital quantum number. 3. The z-component of the angular momentum must be one of the values The integer m is called the magnetic quantum number. Each stationary state of the hydrogen atom is identified by a triplet of quantum numbers (n, l, m).

19 The quantum number n is the number of nodes in radial direction. The quantum number l is the number of nodes in theta. The quantum number m is the number of nodes in azimuth. Subtle classical correlation: Orbital angular momentum is conserved and can be related to l and m. The wave factor exp(-im phi) implies spatial variation around the z axis and current density proportional to m.

20 Wave representing electron Wave representing electron Electron wave extends around circumference of orbit. Only integer number of wavelengths around orbit allowed. Bohr s wave is the azimuthal factor in the complete wave mechanics solution.

21 The Bohr model computes energy independent of orbit orientation. The full wave theory of spherically symmetric bound states in 3-d and finds an increasing number of states as the radius (n) increases. It is a peculiarity of the Coulomb potential that states with different angular momentum may have the same energy. This is NOT true for a multielectron atom for which the effective potential is not 1/r.

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24 Hydrogen atom: Lowest energy (ground) state 1s-state n =1, = 0, m = 0 Spherically symmetric. Probability decreases exponentially with radius. Shown here is a surface of constant probability

25 n=2: next highest energy 2s-state 2p-state 2p-state n = 2, = 0, m = 0 n = 2, =1, m = 0 n = 2, =1, m = ±1 Same energy, but different probabilities

26 n=3: two s-states, six p-states and 3s-state n = 3, = 0, m = 0 3p-state 3p-state n = 3, =1, m = 0 n = 3, =1, m = ±1

27 ten d-states 3d-state 3d-state 3d-state n = 3, = 2, m = 0 n = 3, = 2, m = ±1 n = 3, = 2, m = ±2

28

29 The probability of finding an electron within a shell of radius r and thickness δr around a proton is where the first three radial wave functions of the electron in a neutral hydrogen atom are

30 Note that the total wavefunction amplitude is complex and both the real and imaginary parts can be positive or negative. None of these four components is readily visualized in 3 dimensions!

31 Notice how the mean radius increases with n as in the Bohr model.

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Solved radial equation: Last time For two simple cases: infinite and finite spherical wells Spherical analogs of 1D wells We introduced auxiliary func

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