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CHEM F111 General Chemistry Lecture 06

Hydrogenic atom: A quantum mechanical
treatment
 Review of lecture 05

• Particle in box – 2D and 3D cases

• Particle on a ring
• Rigid rotor (particle on a spherical surface)
• 1D Harmonic oscillator

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 1D Quantum harmonic oscillator
(revision)

Schrödinger equation for 1-D harmonic oscillator is given by:

2
ℏ 2 d ψ( x) 1 2
− + kx ψ( x)=E ψ ( x) (Eq 1)
2 m dx 2 2

Boundary conditions? ψ(∞)=0=ψ(−∞)

d 2 ψ( x) (2 mE−mkx 2 ) (Eq 2)
We rearrange Eq 1 to get: 2
+ 2
ψ( x)=0
dx ℏ

Now, we make substitutions: k/m=ω2; λ=2E/(ħω);

λ=2E/(ħω) α=mω/ħ;
α=mω/ħ y=α½x ; solve and
simply to get

d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy

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 1D harmonic oscillator
(revision)
d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy
The solution of this equation is a bit involved and we will not solve it here. The
solutions to the above equation have the form:
− y2 / 2
ψv ( y)=N v H v ( y )e ; v=0,1,2 ,…

where, v is vibrational quantum number, Hv(y)(y is Hermite polynomial in y of

degree v, Nv is normalization constant for the wavefunction of the vth state.
The energy levels are non-degenerate and are given by:
1
E v =(v + )h υ; v=0,1,2 ,…; υ is fundamental vibrational frequency .
2

1 k
υ=
2π m√
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1D harmonic oscillator
(revision)

Hermite polynomials can be easily obtained using the following formula:

v − y2
d (e )
v y
2

H v ( y )=(−1) e v
; v=0,1,2 ,…
dy

H 0 ( y )=1
H 1 ( y)=2 y
H 2 ( y)=4 y 2 −2
H 3 ( y )=8 y 3 −12 y
H 4 ( y)=16 y 4 −48 y 2 +12
H 5 ( y)=32 y 5 −160 y 3 +120 y

ψ v ( y)=N v H v ( y )e
− y2 / 2 1
E v =(v + )h υ
2
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1D HO: Wavefunctions and probability
distribution (revision)

v=3
v=3

v=2
v=2
v=1
v=1

v=0 v=0

Ψ (not to scale)
Ψ*Ψ
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1D harmonic oscillator: characteristic
features (revision)

●
The wavefunctions are alternately even and odd functions corresponding
to the even and odd values of v (vibrational quantum number).
●
Number of nodes = v, no nodes for the ground state
● Ev=(v+½)hυ; Zero point energy E0= ½ hυ
●
For ground state, probability density is maximum at mean position. As v
increases, the probability density max gradually shifts towards the
turning points – classical limit obtained as v→∞

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 Rotation of sphere (revision)

Polar and azimuthal angles:

r =( x 2 + y 2 +z 2 )1/ 2 z =r cos θ
−1 z x=r sin θ cos ϕ
θ=cos
( x 2 + y 2 + z2 )1/2 y=r sin θ sin ϕ
y π −1 y
(
ϕ= 1−
|y| 2 ) +tan
x

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 Rotation of sphere (revision)

Particle constrained to rotate on surface of sphere of radius R (rigid rotor)

Classically, KE for rotational motion = J2/2mR2

Schrödinger equation involves the polar angle θ and the azimuthal angle φ as
variables

On solving, and imposing the appropriate boundary conditions, obtain the

‘spherical harmonics,’ Yl,m (θ,φ),
(θ,φ) characterized by two quantum numbers l and ml.
l

The spherical harmonics are a product of two functions,

Yl,m (θ,φ) = Θl,m (θ)Φm (φ);

(φ)
l l l

ml = -l, -l+1,..0,..l-1, l;
l for given l, (l= 0,1,2,3,....)

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 Quantization of the angular
momentum

The orbital angular momentum quantum number l can take on the values 0,1,2,3,...
The magnitude of the angular momentum in the corresponding state is [l(l+1)]1/2ħ
Any spatial component, say z-component of the angular momentum, may only take
one of the values, mlħ, where for a given l, ml may take any integer value from -l to
l.
In other words, the angular momentum vector may only make one out of a discrete
set of 2l+1 angles with any chosen axis in space, say the z-axis

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What if the rotor is not rigid?

Kinetic energy due to rotation on sphere of a given radius will have the form similar
to the one in rigid rotor.

Additionally, there will be a contribution due to radial motion.

Potential energy? PE is in general, the function of coordinates of the particle

V(x,y,z) → V(r, θ, φ) (spherical polar coordinates)

Special Case: Central force field - Spherically symmetric potential – potential

energy is dependent on r alone : V(r) - independent of the direction (θ, φ).

Example: hydrogenic atom.

What is a hydrogenic atom? One-electron atom

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Spherical polar coordinates

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Operator forms in spherical polar
coordinates
ℏ2 ∂ 2 ∂
K.E. Operator for radial motion: − 2
2μ r ∂ r
r(∂r )
K.E. Operator for angular motion: L2/2I

Angular KE operator is expressed as:

This term arises
ℏ2 1 ∂ 1 ∂2
− 2
[
2μ r sin θ ∂ θ (
sin θ
∂
∂
θ
+ 2 )
sin θ ∂ ϕ
2
] from the square of
the z-component of
angular momentum

2
Potential energy operator: V (r )=− Ze
4 π ε0 r
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Schrödinger equation for hydrogenic
atom
Potential energy is only due to the coulombic attraction between the electron
and the nucleus

Spherical polar coordinate system is the most suitable for solving the
Schrödinger equation for hydrogenic atom:

2
ℏ 1 ∂ 2 ∂ψ 1 ∂ 1 ∂2 ψ Ze 2
−
[
2μ r ∂ r
2
r ( + 2 )
∂ r r sin θ ∂θ
sin θ
∂ψ
(+ 2 2 )
∂θ r sin θ ∂ ϕ2 ] −
4 π ϵ0 r
ψ =E ψ

KE acting on ψ PE acting on ψ

It can be proven that the quantity in the square bracket is ∇ 2 ψ

2 ∂ 2 ψ ∂ 2 ψ ∂2 ψ
∇ ψ= 2 + 2 + 2
∂x ∂y ∂z
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Hydrogenic atom wavefunctions

The wavefunctions for the hydrogenic atom, in spherical polar coordinates,

may be shown to factor as

ψ(r, θ, φ) = R(r) Θ(θ) Φ(φ) = R(r) Y(θ,φ)

Further, the requirement that the wavefunction be well-behaved, (ie., single

valued, continuous,..) leads to the result that the functions are labeled by
three quantum numbers n, l, and ml ie.,

ψn,l,m (r,θ,φ) = Rn,l(r)Θl,m (θ)Φm (φ) = Rn,l(r)Yl,m (θ, φ)

l l l l

where Rn,l(r) is the radial part of ψ (radial function), and Yl,m (θ,φ) is its
l
angular part – the spherical harmonic.
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Hydrogenic atom wavefunctions

Definition: Orbital is a one-electron function.

Atomic orbital is a one-electron function for an atom.

We see that, the wavefunctions of hydrogenic atom are atomic orbitals.

Hydrogenic orbitals that are characterized by three quantum numbers* n, l,

and ml

Why three quantum numbers ?

The maximum number of physical quantities that can simultaneously be precisely

specified is three, namely, the energy, the magnitude of the angular momentum,
and one of its spatial components. The corresponding quantum numbers arise
when the conditions to be fulfilled by the wavefunction are imposed in the three
dimensions
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Energy levels

Energy – Depends on principle quantum number, n.

Obtained as Hamiltonian eigenvalues: H^ ψn ,l , m (r ,θ, ϕ)=E n ψ n ,l ,m (r ,θ ,ϕ)
l l

μ e4 Z 2
E n =− 2 2 2 2
; n=1,2,3 ,…
32 π ε 0 ℏ n
Note that energy doesn't depend on l and ml.
Energy expression coincides with the Bohr model result.
The principle quantum number, n, imposes bound on the azimuthal quantum
number, l, (l=0,1,2,...n–1), which in turn imposes restriction on the orbital
magnetic quantum number, ml, (ml= -l, -l+1, …, 0, …, l–1, l).
The energy of a hydrogenic wavefunction depends only on the principle quantum
number, and is independent of the azimuthal and the orbital magnetic quantum
numbers.
Degeneracy with respect to
●
energy (Hamiltonian eigenstates): n2 *
●
Angular momentum: 2l + 1
●
Component of angular momentum – non-degenerate *
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Angular momentum – magnitude

Magnitude of Angular momentum – orbital angular momentum

quantum number (or azimuthal quantum number), l.

Hydrogenic orbitals are also eigenfunctions of L2 operator:

L2ψn,l,m = l(l + 1)ħ2 ψn,l,m

l l

Thus, the magnitude of orbital angular momentum is

|L| = [l(l + 1)]1/2ħ; l = 0,1,2,...., n–1;

n–1 for given n.

For given l, the orbitals are (2l+1)-fold

(2l+1) degenerate wrt L2.
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Angular momentum – orientation

Orientation of L wrt +ve z-direction – (orbital) magnetic quantum

number ml.
The orbitals can be chosen* to be simultaneously, the eigenfunctions
of Lz operator: Lz ψn,l,m = mlħψn,l,m
l l

The angular momentum vector is oriented such that the eigenvalues:

Lz = mlħ ; ml = -l,-l+1,...,0,...,l-1,l; for given l.
Degeneracy: The orbitals are non-degenerate wrt Lz.

*more, later.

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Example: l = 1, ml = 1,0,-1

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Example: l = 2, ml = 2,1,0,-1,-2

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Shells, subshells and orbitals

What values can the quantum numbers take ?

n = 1, 2, 3,…..
Shell is determined by n (characterized by energy)
l = 0, 1, 2,.., n-1,
n-1 for given value of n
For a given shell (that is, for a given n), there are n subshells. Each
subshell is characterized by the radial wavefunction, Rn,l(r); (r) l
=0,1,2,3,4,5,... corresponds to s, p, d, f, g, h,.... subshells of a given
shell. Maximum value of l is n–1.
n–1
For a given subshell (that is, for a given {n,l}),
{n,l} there are 2l+1 orbitals
corresponding to ml=-l, -l+1, …, 0, …, l–1, l.l
How many orbitals for a given n? → n2

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Hydrogenic orbitals-characteristics

The general form is ψn,l,m (r,θ,φ) = Rn,l(r)Yl,m (θ, φ)

l l

Number of radial nodes is determined from the Radial function and equals
to the degree of polynomial in r.

Azimuthal quantum number equals to Principle quantum number

number of angular nodes

Yl,ml(θ, φ) are spherical harmonics: Polynomial of degree, “l” in cosθ and/or

sinθ multiplied by Φml(φ)

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Spherical Harmonics (FYI)

The spherical harmonics, Yl,m (θ,φ),

θ,φ) provide the angular parts of the hydrogenic
l
orbitals, that is, hydrogenic wavefunctions. These are expressible as product of the
polar (θ-dependent) and the azimuthal (φ-dependent) parts.
Y l, m (θ, ϕ)=Θl, m (θ) Φ m ( ϕ)
l l l

Θ0,0 (θ)=N 0,0

Θ1,0 (θ)= N 1,0 cosθ
Θ1,±1 (θ)= N1,1 sin θ
±i m l ϕ
2 Φ±m (ϕ)=e
Θ2,0 (θ)=N 2,0 3 cos θ−1 l

'
Θ2 ,±1 (θ)=N 2,1 sin 2 θ≡N 2,1 sin θ cosθ
2
Θ2 ,±2 (θ)= N2,2 sin θ
3
Θ3,0 (θ)=N 3,0 5 cos θ−3 cos θ
Θ3, ±1 (θ)= N3,1 sin θ(5cos 2 θ−1)
Θ3, ±2(θ)=N 3,2 sin 2θ cosθ
3 (The Nl,|m |’s are the normalization constants)
Θ3, ±3(θ)=N 3,3 sin θ l

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Orbitals with zero orbital angular
momentum
The wavefunctions corresponding to l=0 are called s-orbitals. They are
independent of of θ and φ. In other words, the angular wavefunction is
constant.
For example,

Note: In all the orbital expressions, the normalization constant, M is distinct.

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Orbitals with angular momentum
vector lying in xy-plane
These orbitals are characterized by ml=0 by virtue of zero z-component of the
angular momentum. These orbitals are independent of the azimuthal angle, φ.
Excluding the s-orbitals (i.e., l=0, since, already discussed), these are
characterized by global maxima of probability density along +z and -z
directions and are symmetric with respect to rotation about the z-axis.
For example,

Note: In all the orbital expressions, M is normalization constant and is

different for different orbitals.
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