Lecture 17: Radial Wavefunction and Orbital Levels of the Hydrogen Atom The material in this lecture covers

the following in Atkins. The structure and Spectra of Hydrogenic Atoms Section 13.1 The structure of hydrogenic atoms (b) The radial solution 13.2 Atomic orbitals and their energies (a) The energy levels (b) Ionization Energies Lecture on-line Hydrogen energy levels and radial wavefunction (PDF Format) Hydrogen energy levels and radial wavefunction (PowerPoint)

z r Ze x

-e (r,,)

Hydrogen Levels

Re view : Quantum numbers of the hydrogenic atom

y

The wavefunction of the hydrogenic atom depends on three quantum numbers (r, , ) = Rnl (r)Yl,m (, )

The principle quantum number : n = 1,2,3,4,.... Angular momentum quantum number : l = 0,1,2,3,..n - 1 Magnetic quantum number : ml = l, l 1, l 2,...., l
E= Z2e4
2 32 2 oh2n2

Re view : Quantum numbers Hydrogen Levels of the hydrogenic atom

z Lz = hml L2 = h 2l(l + 1) y x
z r v v v L= r v y v x

Angular momentum quantum number : l = 0, 1, 2, 3, ..n - 1 is related to the length L of the angular momentum of the electron as it moves around nucleus
Magnetic quantum number : ml = l, l 1, l 2, ...., l r is related to the length of the projection of L on to r an arbitrary vector (e z ) .

z r Ze x

Hydrogen -e
(r,,)

Levels

Re view : Radial wavefunction R nl (r) of the hydrogenic atom

y

The wavefunction of the hydrogenic atom is given by : (r, , ) = R(r)nl Yl,m (, )

With the radial part given as l R nl (r) = N nl Ln,l (r)e / 2n n

Normalization

Polynomial

Exponential

Hydrogen Levels

n=1 ; l=0

Re view : Radial wavefunction R nl (r) of the hydrogenic atom

No nodes. R1,0 (r ) everywhere positive

R10 (0) 0

2Zr = ao Z R1,0 (r ) = 2 ao
3/2

and

ao =

4 oh2 me e2

e / 2

Hydrogen Levels

Re view : Radial wavefunction R nl (r) of the hydrogenic atom

Only Rnl (r ) with l = 0 has Rnl (o) 0

R2,0 (r ) : one node R2,1(r ) : zero nodes

2Zr = ao

and

ao =

4 oh2 me e2

1 Z R20 (r ) = 2 2 ao

3/2

1 Z 1 / 4 R 2,1 (r) = (2 )e 4 6 ao 2

3/2

e / 4

Hydrogen Levels

Re view : Radial wavefunction R nl (r) of the hydrogenic atom

R30 (r ) : 2 nodes R31(r ) : 1 node

1 Z R30 (r ) = 9 3 ao

3/2

1 2 / 6 (6 2 + )e 9 1 Z R31(r ) = 27 6 ao
3/2

1 (4 )e / 6 3

Only Rnl (r ) with l = 0 has Rnl (o) 0

Hydrogen Levels

Re view : Radial wavefunction R nl (r) of the hydrogenic atom

No nodes. R3,0 (r ) everywhere positive

In general number of nodes n - l - 1

1 Z R3,2 (r ) = 2 e / 6 81 30 ao Only Rnl (r ) with l = 0 has Rnl (o) 0

3/2

Orbitals of Hydrogenic Atom..PE vz. KE. The balance of kinetic and potential energies that accounts for the structure of the ground state of hydrogen (and similar atoms).

(b) the mean kinetic energy is low, but the potential energy is not very favourable; ; (c) the compromise of moderate kinetic energy and moderately favourable potential energy.

1 V(r) = r

(a) The sharply curved but localized orbital has high mean kinetic energy, but low mean potential energy

Hydrogen Levels

The energy levels of the hydrogen atom showing the subshells and (in square brackets) the numbers of orbitals in each subshell. In hydrogenic atoms, all orbitals of a given shell have the same energy.

E= -

Z2e4
2 32 2 oh2n2

he organization of orbitals n = 1,2,3,4,.... nto subshells l = 0,1,2,3,..n - 1 characterized by I) ml = l, l 1, l 2,...., l and shells characterized by n).

Hydrogen Levels The energy is related to n by

En =

hcR Z n
2

hcR Z =

Z 2 Z e 4
2 32 2 oh 2

meMZ Z = me + M Z The reduced mass

For the hydrogen atom with Z = 1

En =

hcR H n
2

hcR H =

He 4
2 32 2 oh 2

Introducing the Rydberg constant R R = me e 4

2 32 2 o h3c

we have R H

H R = me

Hydrogen Levels

Special feature on measuring the ionization potential of the hydrogen atom from its Lyman emission spectrum

R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4 n=5 n=4 n=3 n=2

Ionization energy I = hcR Energy required to remove electron from groundstate H - - > H+ + e I

Emission : Excited electrons return to ground state

R -hcR

n=1

Hydrogen Levels

R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4 n=5 n=4 n=3 n=2

R -hcR

n=1

Hydrogen Levels

R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4

Energy changes E(n 1) due to emission to groundstate n=5

n=4 n=3 n=2 hcR E(2 1) = + hcR hcR 4 E(3 1) = + hcR 9 hcR E(4 1) = + hcR 16 hcR E(n 1) = 2 + hcR n n=1

R -hcR

Hydrogen Levels
R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4

Frequency of light (n 1) due to emission to groundstate Energy of light h(n 1) due to emission to groundstate n=5
n=4 n=3 n=2 hcR E( 2 1) = + hcR = h( 2 1) 4 hcR E( 3 1) = + hcR = h( 3 1) 9 hcR E(4 1) = + hcR = h(4 1) 16 hcR E(n 1) = 2 + hcR = h(n 1) n n=1

R -hcR

Hydrogen Levels
R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4

Energy of light h(n 1) due to emission to groundstate

Also (n 1) (n 1) = c or t n=5 (n 1) = c/ (n 1) = c(n 1) where t n=4 1/ (n 1) = (n 1) n=3 Thus h(n 1) = hc(n 1)

R -hcR

n=2 hcR t E( 2 1) = + hcR = hc( 2 1) 4 hcR E( 3 1) = + hcR = hc( 3 1) 9 t hcR E(4 1) = + hcR = hc(4 1) 16 hcR t E(n 1) = 2 + hcR = hc(n 1) n n=1

Hydrogen Levels

E(n 1) = = hc(n 1)

hcR n2

+ hcR

R -hcR 25 R -hcR 16 R -hcR 9 R -hcR 4 n=5 n=4 n=3 n=2

hcR n2

+ I = hc(n 1) R

I (n 1) = + 2 hc n

I R (2 1) = + 4 hc

82 250 cm-1
97 492 cm-1

R I (3 1) = + 9 hc
I R (4 1) = + 16 hc n=1

102 824 cm-1

R -hcR

Hydrogen Levels Slope = -R R

R I 1) = + (n n 2 hc
I R + 16 hc
I R + 9 hc

(4 1) =

102 824 cm-1 97 492 cm-1

(3 1) =

R I (2 1) = + 4 hc

82 250 cm-1

Intercept = I/hc

What you need to know about the hydrogen atom from the previous lecture 1. You are not expected to be able You should also be aware of to solve the Schrdinger equation for the following commutation the hydrogen - like atom relations
Hn,l,m ( r , , ) = En n,l,m ( r , , )
However you should be aware that the Hamiltonian can be written in the form r 1 h2 2 2 Ze ]+ H= [ 2 + L2 4 o r 2 r r r 2r 2 where r is the distance between the hydrogen - like atom and the electron whereas is the reduced mass.

[H, L2 ] = 0 and [H, Lz ] = 0

What you need to know about the hydrogen atom from the previous lecture
2. You are not required to memorize the exact form of the eigenfunctions.

You should recognized that they can be written as a product of a radial part Rnl (r) and the spherical harmonics Ylm (, ) [eigenfunctions of L2 and Lz ] as n,l,m (r, , ) = R nl (r)Ylm (, )

with the corresponding energies given by Z2me 4

2 32p2 e o h 2 n 2

E= -

It is important that you remember the possible quantum numbers for l and m with respect to a given n.

What you need to know about the hydrogen atom from this lecture

3. You should be able to count the number of nodes in R n,l ( r ) as n - l - 1 and realize that Rn,l ( r ) only is different from zero at the nucleus for l = 0.
4. You are expected to relate the l and m quantum numbers to the length of the orbital angular momentum vector and the projection of the orbital angular momentum vector on the arbitrary z - axis, respectively.
5. Review the way in which absorption spectra, emission spectra and ionization potentials for the hydrogen atom are derived from the energy levels En and make note of the degeneracy of the energy levels En (subshell structure)