A Closer Look at

Contains Information about the Probability of finding the Quantum Mechanical Entity in a Certain State
For atom, know energy so is related to probability of finding electron at a certain point in space

The Probability is not , rather 2

Actually this is *

More on Orbitals
Wavefunctions for Atomic Orbitals can be divided into Two Parts
Radial (depends on distance from nucleus) Angular (depends on angles and )

For Chemistry Angular Part is (most) Important

Molecular shape Bonding

Nodes
Places where the Probability of finding the Electron is Zero ( = 0 so 2 = 0 ) When radial is zero, called a radial (or spherical) node
There are n - l - 1 radial nodes

When angular is zero, called an angular node (or a nodal plane)

There are l angular nodes

1s Radial Wavefunction
1.2 1.0

radial

(arbitrary units)

0.8

Z = 2 a 0

3/ 2

e Zr / a0

0.6

There are n - l - 1 = 1 - 0 - 1 = 0 radial nodes. Note that 0 at x = 0.

0.4

0.2

0.0 2 -0.2 4 6 8 10 12 14 16

Distance from Nucleus (arbitrary units)

1s Orbital

2s Radial Wavefunction
1.2 1.0

radial

(arbitrary units)

0.8

1 Z = 2 2 a0

3/ 2

Z 2 a0

r e Zr / 2 a0

0.6

There are n - l - 1 = 2 - 0 - 1 = 1 radial node. Note that 0 at x = 0.

0.4

0.2

0.0 2 -0.2 4 6 8 10 12 14 16

Distance from Nucleus (arbitrary units)

2s Orbital

3s Radial Wavefunction
1.2 1.0

radial

1 Z = 9 3 a0

3/ 2

(arbitrary units)

0.8

4Z 2Z 2 2 Zr / 3 a0 6 a r + 3a r e 0 0

0.6

There are n - l - 1 = 3 - 0 - 1 = 2 radial nodes. Note that 0 at x = 0.

0.4

0.2

0.0 2 -0.2 4 6 8 10 12 14 16

Distance from Nucleus (arbitrary units)

3s Orbital

10

Probability of Finding an Electron

Remember 2, not , is Probability
1.2

2 for 1s, 2s and 3s orbitals Note s orbitals have a non-zero probability of being found at the nucleus.

2 (arbitrary units)

1.0 0.8 0.6 0.4 0.2 0.0 0 2 4 6 8 10 12 14 16

Distance from the Nucleus (arbitrary units)

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Probability of Finding an Electron

0.10

1s
2 (arbitrary units)
0.08

2s
0.06

Note wherever there was a node 2 = 0, there is no probability that the electron can be found there.

0.04

3s If the electron cant be in a certain place, how does it get across?

0.02

0.00 0 2 4 6 8 10 12 14 16

Distance from the Nucleus (arbitrary units)

12

Radial Distribution Function

Problem with 2, it over estimates Probability Close to Nucleus and under estimates it Further Out Correct by multiplying 2 by 4r2
Takes into account that a wedge is smaller toward the center than ends This correction only works for s orbitals

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Radial Distribution Function

6

Electrons in orbitals with higher n are usually found further from nucleus. 2s 3s Note that 2s and 3s electrons have probability of being closer to nucleus than 1s!

4 r2 2 (arbitrary units)

1s

0 0 2 4 6 8 10 12 14 16

Distance from Nucleus (arbitrary units)

14

1s, 2s, and 3s orbitals

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Angular Part of Wavefunction

Every Time goes through a node Sign of Wavefunction changes
s orbital has same angular sign throughout p orbital lobes have different signs Lobes alternate signs in a d orbital

Difference in Phase

p orbital

d orbital

dz2 orbital

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p Orbitals
Typical p orbital Typical p orbital

When n = 2, then ll = 0 and 1 When n = 2, then = 0 and 1 Therefore, in n = 2 shell there Therefore, in n = 2 shell there are 2 types of orbitals (2 are 2 types of orbitals (2 subshells) subshells) For ll = 0 ml l = 0 For = 0 m = 0 this is a s subshell this is a s subshell For ll = 1 ml l = --1, 0, +1 For = 1 m = 1, 0, +1 this is a p subshell this is a p subshell with 3 orbitals with 3 orbitals

planar node planar node

When l = 1, there is a PLANAR NODE thru the nucleus.

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p Orbitals

A p orbital

The three p orbitals lie 90o apart in space

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2p Radial Wavefunction
1.2

radial

1 Z = 4 6 a0

3/ 2

2Z a 0

r e Zr / 2 a0

1.0

(arbitrary units)

0.8

There are n - l - 1 = 2 - 1 - 1 = 0 radial nodes. Note that = 0 at x = 0. Only s orbitals have any probability density at the nucleus.

0.6

0.4

0.2

0.0 2 -0.2 4 6 8 10 12 14 16

Distance from Nucleus (arbitrary units)

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2px Orbital

20

2py Orbital

10

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2pz Orbital

22

Degenerate 2p Orbitals
All 3 orbitals have the same energy (n and l), but differ in orientation (ml)

11

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3p Radial Wavefunction
0.10

radial

0.08

1 Z = 27 6 a0

3/ 2

2 Z 2 Z 4 3a r a 0 0

r e Zr / a0

0.06

radial ((Z/a0)3/2)

0.04

Number of radial nodes = n - l - 1 Number of radial nodes = 3 - 1 - 1 = 1

0.02

0.00 5 -0.02 10 15

Distance from Nucleus (Zr/a0)

20 25 30

-0.04

24

3px Orbital

12

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3py Orbital

26

3pz Orbital

13

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d Orbitals
When n = 3, what are the values of l? l = 0, 1, 2 so there are 3 subshells in the shell. For l = 0, ml = 0 ---> s subshell with single orbital For l = 1, ml = -1, 0, +1 ---> p subshell with 3 orbitals For l = 2, ml = -2, -1, 0, +1, +2 ---> d subshell with 5 orbitals

28

d Orbitals
typical d orbital planar node

planar node

s orbitals have no planar nodes (l = 0) and are spherical. p orbitals have l = 1, have 1 planar node, and are dumbbell shaped. This means d orbitals (l = 2) have 2 planar nodes

14

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3d Radial Wavefunction
0.05

0.04

radial

radial ((Z/a0)3/2)

1 Z = 81 30 a0

3/ 2

2 Zr Zr / 3a0 a e 0

0.03

Number of radial nodes = 0

0.02

0.01

0.00 0 5 10 15 20 25 30 35

Distance from Nucleus (Zr/a0)

30

3dxy Orbital

15

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3dxz Orbital

32

3dyz Orbital

16

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3dz2 Orbital

34

3dx2-y2 Orbital

17

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d Orbitals

36

f orbitals
When n = 4, l = 0, 1, 2, 3 so there are 4 subshells in the shell. For l = 0, ml = 0 s subshell with single orbital For l = 1, ml = -1, 0, +1 p subshell with 3 orbitals For l = 2, ml = -2, -1, 0, +1, +2 d subshell with 5 orbitals For l = 3, ml = -3, -2, -1, 0, +1, +2, +3

f subshell with 7 orbitals

18

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f orbitals

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