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5.111 Principles of Chemical Science

Fall 2008
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5.111 Lecture Summary #6
Readings for today: Section 1.9 (1.8 in 3rd ed) Atomic Orbitals.
Read for Lecture #7: Section 1.10 (1.9 in 3rd ed) Electron Spin, Section 1.11 (1.10 in 3rd
ed) The Electronic Structure of Hydrogen.
_______________________________________________________________________________
Topics: Hydrogen Atom Wavefunctions

I. Wavefunctions (orbitals) for the hydrogen atom (H = E )
II. Shapes of H-atom wavefunctions: s orbitals
III. Radial probability distributions
________________________________________________________________________________
ENERGY LEVELS (continued from Lecture #5)
The Rydberg formula can be used to calculate the frequency (and also the E or ,
using E = h or = c/ ) of light emitted or absorbed by any 1-electron atom or ion.
nf > ni in ___________________. Electrons absorb energy causing them to go from a lower

to a higher E level.
ni > nf in ___________________. Electrons emit energy causing them to go from a higher to

a lower E level.
I. WAVEFUNCTIONS (ORBITALS) FOR THE HYDROGEN ATOM
When solving H = E, the solutions are En and (r,,).
(r,,) stationary state wavefunction: time-independent

In solutions for (r,,), two new quantum numbers appear! A total of 3 quantum
numbers are needed to describe a wavefunction in 3D.
1. n principal quantum number

n = 1, 2, 3
determines binding energy
2. l angular momentum quantum number
l = _____________________________________
l is related to n
largest value of l = n 1
determines angular momentum
3. m magnetic quantum number
m = _____________________________________
m is related to l
largest value is +l, smallest is l
determines behavior of atom in magnetic field
To completely describe an orbital, we need to use all three quantum numbers:
nlm(r,,)
The wavefunction describing the ground state is ________________ .
Using the terminology of chemists, the 100 orbital is instead called the ___ orbital.
An orbital is (the spatial part) of a wavefunction; n(shell) l(subshell) m(orbital)
l = 0 ___ orbital l = 1 ___ orbital l = 2 ___ orbital l = 3 ___ orbital
for l = 1: m = 0 _____ orbital, m = 1 states combine to give ____ and ____ orbitals
State label wavefunction orbital En En[J]

n=1
l =0 100 RH/12 2.18 1018J
m=0
n=2
l =0 -5.45 1019J
m=0
n=2
l =1 -5.45 1019J
m = +1
n=2
l =1 210 210 RH/22 -5.45 1019J
m=0
n= 2
l =1 21-1 21-1 RH/22 -5.45 1019J
m = -1
For a ____________, orbitals with the same n value have the same energy: E = -RH/n2.
Degenerate having the same energy

For any principle quantum number, n, there are _______ degenerate orbitals in
hydrogen (or any other 1 electron atom).
2
Energy Level Diagram 9 degenerate states at second
E [J] excited energy level
_____ ______ ______ ______ ______ ______ ______ ______ ______

-0.242 1018 n=3 3 3 3 3 3 3 3 3
l =0 l =1 l =1 l =1 l =2 l =2 l =2 l =2 l =2
m=0 m=1 m=0 m=1 1, 2 1, 2 m = 0 1, 2 1, 2
______ ______ ______ ______ 4 degenerate states at first excited

-0.545 1018 n=2 2 2 2 energy level
l =0 l =1 l =1 l = 1
m=0 m=1 m=0 m=1
______
-2.18 1018
1 state at ground energy level
n = 1 1s state described by 100 or 1s
l = 0
m = 0
II. SHAPES OF H-ATOM WAVEFUNCTIONS: S ORBITALS
THE PHYSICAL INTERPRETATION OF A WAVEFUNCTION
Max Born (German physicist, 1882-1970). The probability of finding a particle (the
electron!) in a defined region is proportional to the square of the wavefunction.
[nlm(r,,)]2 = PROBABLITY DENSITY

probability of finding an electron per unit volume at r, ,
To consider the shapes of orbitals, lets first rewrite the wavefunction as the product of a
radial wavefunction, Rnl(r ), and an angular wavefunction Ylm(,)
nlm(r,,)] = _________ x _________
for a ground state H-atom:
where a0 = ____________________________ (a constant) = 52.9 pm
For all s orbitals (1s, 2s, 3s, etc.), the angular wavefunction, Y, is a ______________.
s-orbitals are spherically symmetrical independent of _____ and_____.
Probability density plot of s orbitals: density of dots represent probability density
2100 (1s) 2200 (2s) 2300 (3s)
z 3s
r = 7.1a0
x
r = 1.9a0
Figures by MIT OpenCourseWare.
NODE: A value for r, , or for which (and 2) = ______. In general, an orbital

has n -1 nodes.
RADIAL NODE: A value for ______ for which (and 2) = 0. In other words, a
radial node is a distance from the radius for which there is no probability of finding
an electron.
In general, an orbital has n - 1 l radial nodes.
1s: 1 1 0= 0 radial nodes
2s: ____ ____ ____ = ____ radial nodes
3s: ____ ____ ____ = ____ radial nodes
III. RADIAL PROBABILITY DISTRIBUTION
Probability of finding an electron in a spherical shell of thickness dr at a distance r

from origin.
Radial Probability Distribution (for s orbitals ONLY) = 4r22 dr

4
We can plot the radial probability distribution as a function of radius.
Radial probability distribution for a hydrogen 1s orbital:
Maximum probability or most probable value of r is denoted rmp.
rmp for a 1s H atom = a0 = 0.529 x 1010 m = 0.529 a0 BOHR radius
1913 Niels Bohr (Danish scientist) predicted quantized levels for H atom prior to
QM development, with the electron in well-

defined circular orbits.
This was still a purely particle picture of the e.
But, an electron does not have well-defined orbits! The best we can do is to find the
probability of finding e at some position r.
Knowing only probability is one of main consequences of Quantum Mechanics.

Unlike CM, QM is non-deterministic. The uncertainty principle forbids us from
knowing r exactly.

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5.111 Principles of Chemical Science

Topics: Hydrogen Atom Wavefunctions

ENERGY LEVELS (continued from Lecture #5)

nf > ni in ___________________. Electrons absorb energy causing them to go from a lower

ni > nf in ___________________. Electrons emit energy causing them to go from a higher to

I. WAVEFUNCTIONS (ORBITALS) FOR THE HYDROGEN ATOM

When solving H = E, the solutions are En and (r,,).

(r,,) stationary state wavefunction: time-independent

1. n principal quantum number

determines binding energy

2. l angular momentum quantum number

determines angular momentum

3. m magnetic quantum number

To completely describe an orbital, we need to use all three quantum numbers:

An orbital is (the spatial part) of a wavefunction; n(shell) l(subshell) m(orbital)

l = 0 ___ orbital l = 1 ___ orbital l = 2 ___ orbital l = 3 ___ orbital

State label wavefunction orbital En En[J]

Degenerate having the same energy

_____ ______ ______ ______ ______ ______ ______ ______ ______

______ ______ ______ ______ 4 degenerate states at first excited

m=0 m=1 m=0 m=1

II. SHAPES OF H-ATOM WAVEFUNCTIONS: S ORBITALS

THE PHYSICAL INTERPRETATION OF A WAVEFUNCTION

[nlm(r,,)]2 = PROBABLITY DENSITY

nlm(r,,)] = _________ x _________

for a ground state H-atom:

where a0 = ____________________________ (a constant) = 52.9 pm

Probability density plot of s orbitals: density of dots represent probability density

2100 (1s) 2200 (2s) 2300 (3s)

NODE: A value for r, , or for which (and 2) = ______. In general, an orbital

In general, an orbital has n - 1 l radial nodes.

1s: 1 1 0= 0 radial nodes

2s: ____ ____ ____ = ____ radial nodes

3s: ____ ____ ____ = ____ radial nodes

III. RADIAL PROBABILITY DISTRIBUTION

Probability of finding an electron in a spherical shell of thickness dr at a distance r

Radial Probability Distribution (for s orbitals ONLY) = 4r22 dr

Maximum probability or most probable value of r is denoted rmp.

rmp for a 1s H atom = a0 = 0.529 x 1010 m = 0.529 a0 BOHR radius

QM development, with the electron in well-

This was still a purely particle picture of the e.

Knowing only probability is one of main consequences of Quantum Mechanics.

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l = 0 _ orbital l = 1 _ orbital l = 2 _ orbital l = 3 _ orbital

_ ____

4 degenerate states at first excited

nlm(r,,)] = _ x _

2s: = radial nodes

3s: = radial nodes