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Pilani Campus
CHEM F111 General Chemistry Lecture 07
Hydrogenic atom: A quantum
mechanical treatment
Review of lecture 06
• Effect of bond-strength and effective mass
on vibrational frequency
• IR spectroscopic analysis of organic
molecules
• Effect of electron-donating and electron-
withdrawing interactions on IR peak
positions and intensities.
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Revisit Rotation of sphere
Polar and azimuthal angles:
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Revisit Rotation of sphere
● 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),
l
characterized by two quantum numbers l and ml.
● The spherical harmonics are a product of two
functions, Yl,m (θ,φ) = Θl,m (θ)Φm (φ);
l l l
ml = -l, -l+1,..0,..l-1, 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, mħ, 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). Specific 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
2
ℏ ∂ r2 ∂
● K.E. Operator for radial motion: −
2mr ∂ r
2
∂r ( )
●
K.E. Operator for angular motion: L 2/2I
Which is expressed as:
This term
[ ]
ℏ
2
1 ∂ ∂ 1 ∂2 arises from
−
2mr sin θ
2 ∂θ (
sin θ
∂ θ )
+ 2
sin θ ∂ ϕ
2 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:
[ ψ ψ ψ
]
2 2 2
∂ 1 ∂ 1 ∂ Ze
−
ℏ
2mr ∂ r
2 (
∂ r2
)+
∂ r sin θ ∂ θ(
∂ sin θ
)+ 2
∂ θ sin θ ∂ ϕ 2
−
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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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:
[
ℏ 1 ∂ 2∂ψ ψ ψ
]
2 2 2
1 ∂ 1 ∂ Ze
−
2m r ∂ r
2 (r )
+
∂ r r sin θ ∂ θ
2 (
∂ sin θ
)
+ 2 2
∂θ r sin θ ∂ ϕ 2
−
4π 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)
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,ml(r,θ,φ) = Rn,l(r)Θl,ml(θ)Φml(φ) = Rn,l(r)Yl,ml(θ, φ)
where Rn,l(r) is called the radial part of ψ (radial
wavefunction), and Yl,ml(θ, φ) is its angular part – the
spherical harmonics.
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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 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, the energy,
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:
Hψn,l,m = Enψn,l,m
l l
En = -μe4Z2/32π2ε02ħ2n2; n = 1,2,3,…
where, μ is reduced mass.
Note that energy doesn't depend on l and ml.
For given n, orbitals are n2-fold degenerate wrt H.
If electron spin is considered, 2n2 states correspond to
same energy En.
Energy expression coincides with the Bohr model
result.
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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 L 2
operator:
L 2ψn,l,m = l(l + 1)ħ2ψn,l,m
l l
Thus, the magnitude of orbital angular momentum is
|L | = [l(l + 1)]1/2ħ; l = 0,1,2,...., n-1; for given n.
For given l, the orbitals are (2l+1)-fold degenerate wrt
L 2.
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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 L z operator: L z ψn,l,m = mlħψn,l,m
l l
The angular momentum vector is oriented such that the
eigenvalues: L z = mlħ ; ml = -l,-l+1,...,0,...,l-1,l; for
given l.
Degeneracy: The orbitals are non-degenerate wrt L z.
*will be discussed later in the lecture
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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, for given value of n
• For a given n, there are n subshells. Each subshell is
characterized by the radial wavefunction, Rn,l(r); l
=0,1,2,3,4,5,... corresponds to s, p, d, f, g, h,....
subshells of a given shell.
• For given l, there are 2l + 1 orbitals corresponding to
ml = -l, -l+1,..,0,..l-1, l.
• How many orbitals for a given n? → n2
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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, M is normalization constant
and is different for different orbitals.
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Orbitals with zero z-component of
orbital angular momentum
These orbitals are characterized by ml=0. 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 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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Orbitals with zero z-component of
orbital angular momentum
Note: In all the orbital expressions, M is normalization constant
and is different for different orbitals.
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Orbitals with non-zero z-component
of orbital angular momentum
These orbitals are characterized by l>0, |ml|>0. If one probes
to measure the exact value of z-component of the angular
momentum in addition to its magnitude, the orbitals are
complex with Φm (φ) = eimlφ
l
For example,
Note: In all the orbital expressions, M is normalization constant
and is different for different orbitals.
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