Chem3420 Topic3 4 New2

-Atomic Systems (Topic 3)
3.1. Hydrogenic Atoms

Outline
1. Atomic Spectrum of Hydrogen
2. Solving Schrödinger Equation of
hydrogenic atoms
3. Atomic orbitals and Energies
4. Shells and subshells
Radial Distribution Functions
For a 1s orbital,
Physical interpretation:
• Because r2 = 0 at the nucleus, P(0) = 0. The volume of
the shell is zero when r = 0 so the probability of finding
the electron in the shell is zero.
• As r → ∞, P(r) → 0 on account of the exponential term. The wavefunction has
fallen to zero at great distances from the nucleus and there is little probability of
finding the electron even in a large shell.
• The increase in r2 and the decrease in

the exponential factor means that P
passes through a maximum at an
intermediate radius; it marks the
most probable radius at which the
electron will be found regardless of
direction.
For a 1s orbital,
Practice
Calculate the most probable radius, rmp, at which an electron will be found
when it occupies a 1s orbital of a hydrogenic atom of atomic number Z,
and tabulate the values for the one electron species from H to Ne9+.
For a 1s orbital,
Practice
You need to find the radius at which the radial

distribution function of the hydrogenic 1s orbital
has a maximum value by solving dP/dr = 0. If there
are several maxima, you should choose the one
corresponding to the greatest amplitude.
For a 1s orbital,
Practice
dP/dr = 0
You need to find the radius at which the radial
distribution function of the hydrogenic 1s orbital
has a maximum value by solving dP/dr = 0. If there
are several maxima, you should choose the one
corresponding to the greatest amplitude.
For a 1s orbital,
Practice
d
( )
dr
d
( )
dr
x=r k = 2Z/a0
+
For a 1s orbital,
Practice
dP/dr = 0
!"
1- =0
This function is zero at r = 0 #!
!"
1=
#!
and at #!
=r
!
Then, with a0 = 52.9 pm, the most probable radii are

For a 1s orbital,
Practice
dP/dr = 0
This function is zero at r = 0
and at
Then, with a0 = 52.9 pm, the most probable radii are

1s orbital of H, Z
rmp = a0,
rmp
the Bohr radius
Notice how the 1s orbital is drawn towards the nucleus as the nuclear charge increases.
At uranium the most probable radius is only 0.58pm, almost 100 times closer than for hydrogen.
(On a scale where rmp = 10 cm for H, rmp = 1 mm for U.) However, extending this result to very
heavy atoms neglects important relativistic effects that complicate the calculation.
Old slide
Shells and Sub-shells
Shell (characterized by principal quantum number n)
It is common to refer to successive shells by letters:
Sub-Shell (characterized by orbital angular momentum quantum number l)

These subshells are also generally referred to by letters:
p Orbitals
Subshell: three 2p orbitals
Orbital angular momentum quantum number l = 1
(specifies the magnitude of the angular momentum)
Magnetic quantum number ml = -1, 0, +1

(specifies the z-component of the angular momentum)
For example, the orbitals with ml = 0 have zero angular momentum around the z-axis.
The wavefunction of a 2p orbital with ml = 0 is .

Old slide
Solving Schrödinger Equation for Hydrogenic Atoms
3. Solving the electronic angular wavefunctions
2
Λ Yl,ml (θ , ϕ ) = −l(l +1)Yl,ml (θ , ϕ )
Schrödinger equation for a particle free to move at constant
radius around a central point:
The allowed solutions are the spherical harmonics specified
by the quantum numbers l and ml.
Spherical harmonics for Schrodinger equation

https://www.youtube.com/watch?v=yRJ2Xf2oH5w&list=PLWt5FuzgdX4nsEeVG4nBdpD
AtIYFq20OG&index=7
Old slide
5. Solving the electronic radial wavefunctions
p Orbitals
(specifies the magnitude of the angular momentum)

z-axis
cos2θ = 1 Higher θ = 0 R2,0 ∝ (2 − ρ )
θ=0
The angular variation is proportional to cosθ.
Lower
None Therefore, the probability density, which is
Lower proportional to cos2θ, has its maximum value
on either side of the nucleus along the z-axis
θ = 180° (at θ = 0 and 180°, where cos2θ = 1).
cos2θ = 1 Higher θ = 180°
p Orbitals

z-axis
cos2θ = 1 Higher θ = 0 R2,0 ∝ (2 − ρ )
θ=0
The wavefunction is zero everywhere in
Lower
θ = 90° None
θ = 90° the xy-plane, where z = 0, so the xy-plane
cos2θ = 0 Lower is a nodal plane of the orbital: the
wavefunction changes sign on going from
θ = 180°
Higher θ = 180°
one side of the plane to the other.
cos2θ = 1
p Orbitals

f(r) is a function only of r.

Spherical polar coordinate is z = r cos θ.
All p orbitals with ml = 0 and any value

of n have wavefunctions of this form,
but f(r) depends on the value of n.
p Orbitals

How about the orbitals with ml = ±1 ?
The wavefunction of a 2p orbital with ml = ±1 is .

Old slide
3. Solving the electronic angular wavefunctions
2
Λ Yl,ml (θ , ϕ ) = −l(l +1)Yl,ml (θ , ϕ )
Schrödinger equation for a particle free to move at constant
radius around a central point:
The allowed solutions are the spherical harmonics specified
by the quantum numbers l and ml.
Spherical harmonics for Schrodinger equation

https://www.youtube.com/watch?v=yRJ2Xf2oH5w&list=PLWt5FuzgdX4nsEeVG4nBdpD
AtIYFq20OG&index=7
Old slide
5. Solving the electronic radial wavefunctions
p Orbitals

How about the orbitals with ml = ±1 ?
z-axis z-axis Zero amplitude at θ = 0 and

sin2θ = 0 None
θ=0 θ=0
180° along the z-axis and
Lower Lower maximum amplitude at 90° in
Higher Higher the xy-plane. Non-zero
θ = 90° θ = 90° θ = 90°
sin2θ = 1 xy-plane angular momentum about the
Lower Lower z-axis: clockwise rotation
θ = 180° θ = 180° and anticlockwise rotation .
sin2θ = 0 None
p Orbitals
To draw the functions by forming the linear combinations (ψ = c1ψ1 + c2ψ2)

c1 and c2 are arbitrary coefficients.
These linear combinations correspond to zero

orbital angular momentum around the z-axis,
(sinθ = 0 at θ = 0 and 180° around the z-axis)
as they are superpositions of states with equal
and opposite values of ml. The px orbital has
the same shape as the pz orbital.
p Orbitals
Subshell: three 2p orbitals with l = 1 and ml = -1, 0, +1.
The wavefunction of any p orbital of a given shell can be written as a product

of x, y, or z and the same function f (which depends on the value of n).
z z
Nodal plane y
y x
z x
x
Old slide
Shells and Sub-shells
Shell (characterized by principal quantum number n)
It is common to refer to successive shells by letters:
Sub-Shell (characterized by orbital angular momentum quantum number l)

These subshells are also generally referred to by letters:
d Orbitals
Subshell: five 3d orbitals
Magnetic quantum number ml = -2, -1, 0, +1, +2
(specifies the z-component of the angular momentum)
The real linear combinations have the following forms, with f(r) depending on n:
d Orbitals
Can you find the angular nodes?

d Orbitals
The two angular nodes divide the orbital into four lobes.
(With the exception of the dz2 orbital)
d Orbitals
(specifies the z-component of the angular momentum)
For the dz2 orbital, the two angular nodes combine to give a conical surface that
separates the main lobes from a smaller toroidal component encircling the nucleus.
Nodes of Atomic Orbitals
R (radial wavefunciton): Y (angular wavefunciton):

electrons move between electrons move around the
concentric surfaces. nucleus on a spherical surface.
Number of
= n-l-1
Radial Nodes
Number of
Angular Nodes
= l
Number of
= n-1
Total Nodes
Total Nodes
n-1
0
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-Atomic Systems (Topic 3)

3.1. Hydrogenic Atoms

• The increase in r2 and the decrease in

You need to find the radius at which the radial

Then, with a0 = 52.9 pm, the most probable radii are

This function is zero at r = 0

Then, with a0 = 52.9 pm, the most probable radii are

Sub-Shell (characterized by orbital angular momentum quantum number l)

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = 0 is .

Spherical harmonics for Schrodinger equation

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = 0 is .

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = 0 is .

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = 0 is .

f(r) is a function only of r.

All p orbitals with ml = 0 and any value

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = ±1 is .

Spherical harmonics for Schrodinger equation

Magnetic quantum number ml = -1, 0, +1

The wavefunction of a 2p orbital with ml = ±1 is .

z-axis z-axis Zero amplitude at θ = 0 and

To draw the functions by forming the linear combinations (ψ = c1ψ1 + c2ψ2)

These linear combinations correspond to zero

The wavefunction of any p orbital of a given shell can be written as a product

Sub-Shell (characterized by orbital angular momentum quantum number l)

Can you find the angular nodes?

Can you find the angular nodes?

Can you find the angular nodes?

R (radial wavefunciton): Y (angular wavefunciton):

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