5.

01x Lecture Summary #7

WAVEFUNCTIONS FOR H ATOM

When solving Ĥψ = Eψ , get En and y(r,q,f,t)

y(r,q,f) º stationary state wavefunction. Time dependence drops out.

In solution for y(r,q,f), two new quantum numbers appear! A total of 3 quantum
numbers needed to describe a wave in 3D.

1. n º principal quantum number

n = 1, 2, 3 … … ¥
determines binding energy

2. ! º angular momentum quantum number

! = 0, 1, 2, 3 … … n – 1
! is related to n
largest value of ! = n – 1
determines angular momentum of e–

3. m º magnetic quantum number

m º 0, ±1, ±2, ±3, … … ±!
m is related to !
largest value is +!, smallest is –!
determines behavior of atom in magnetic field

7.1
 State label wavefunction orbital En En[J]
n=1
!=0 100 state Y100 1s –RH/12 –2.18 ´ 10–18J
m=0
n=2
!=0 200 state Y200 2s –RH/22 -5.45 ´ 10–19J
m=0
n=2
!= 1 211 state Y211 2p –RH/22 5.45 ´ 10–19J
m=1
n=2
!=1 210 state Y210 2p –RH/22 5.45 ´ 10–19J
m=0
n= 2
!=1 21-1 state Y21-1 2p –RH/22 5.45 ´ 10–19J
m = -1

An orbital is (the spatial part of) a wavefunction: n!m

Orbitals are named based on value of !
! = 0 Þ s orbital; ! = 1Þ p orbital; ! = 2 Þ d orbital; ! = 3 Þ f orbital

Energy Level Diagram

9 degenerate states at second excited
E [J] energy level

3s 3py 3pz 3px 3dxy 3dyz 3dz2 3dxz 3dx2-y2

-0.242 ´ 10–18 n=3 3 3 3 3 3 3 3 3
!=0 1 1 1 2 2 2 2 2
m=0 -1 0 1 -2 -1 0 1 2

2s 2py 2pz 2px

-0.545 ´ 10 –18
n=2 2 2 2 4 degenerate states at first
!=0 1 1 1 excited energy level
m=0 -1 0 1

1s
–18
-2.18 ´ 10 n=1 1 state at ground energy level
!=0 1s state described by y100 or 1s
m=0
7.2
degenerate º have the same energy n2 degenerate states at each n
n2 wavefunctions or orbitals that describes the states at each n.

What do the H atom wavefunctions look like?

Each state has 3 labels or quantum numbers, n!m. Each state has a yn!m. General form of
H atom wavefunctions
yn!m(r,q,f) = Rn!(r)Y!m(q,f)

Rn!(r) º radial part, function only in r. Y!m(q,f) º angular part, function in q,f

yn!m = Rn!(r) • Y!m(q,f)

3/2 1/2
⎛ 1 ⎞ ⎛ 1 ⎞
=
−r a 0
y100 2⎜ ⎟ e •⎜ ⎟
⎜⎝ a ⎟⎠ ⎝ 4π ⎠
0
3/2 1/2
1 ⎛ 1 ⎞ ⎛ r ⎞ −r 2a 0 ⎛ 1 ⎞
y200 = ⎜ ⎟ ⎜2 − ⎟e •⎜ ⎟
2 2 ⎜⎝ a ⎟
0⎠
⎜⎝ a 0 ⎟⎠ ⎝ 4π ⎠

⎛ 1 ⎞
3/2 ⎡ ⎛ r ⎞ ⎤ −r 3a
2 1/2
2 ⎢27 − 18 r ⎛ 1 ⎞
y300 = ⎜ ⎟ + 2⎜ ⎟ ⎥ e 0
•⎜ ⎟
⎢ ⎥
81 3 ⎜⎝ a 0 ⎟⎠ ⎣
a0 ⎜ ⎟
⎝ a0 ⎠ ⎦ ⎝ 4π ⎠

ε oh2
where a0 = = 0.529 ´ 10–10 m º Bohr radius
2
πe m

NOTE: 1s, 2s, 3s have no angular dependence — SPHERICALLY SYMMETRIC

Only 1 variable to worry about, r. Let’s plot these waves (orbitals) as a function of r.

7.3