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CHEM F111 General Chemistry Lecture 08

Hydrogenic atom: A quantum
mechanical treatment (continued)
 Review of lecture 07

• Central force field and spherical polar coordinates

• Schrӧdinger equation for Hydrogenic atom
• Radial wavefunctions and spherical harmonics
• Quantum numbers, quantization in energy and
magnitude and orientation of angular momentum
• Shells, subshells, orbitals
• Orbital characterization, Radial and angular nodes

• Form of the wavefunctions with for ml=0 and ml≠ 0

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Hydrogenic orbitals (revision)

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, (i.e., 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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Shells, subshells and orbitals
(revision)
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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Hydrogenic orbitals-
characteristics
The general form is ψn,l,ml(r,θ,φ) = Rn,l(r)Yl,ml(θ, φ)

Number of radial nodes = degree of polynomial in r

Azimuthal quantum number Principle quantum

equals to no of angular nodes number

Yl,m (θ, φ) are spherical harmonics: Polynomial of degree,

l

“l” in cosθ and/or sinθ multiplied by Φml(φ)

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Orbitals with ml=0 (revision)
Orbitals with ml=0, l=0

Orbitals with ml=0, l=1

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Orbitals with ml=0 (revision)

Orbitals with ml=0, l=2,3

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Orbitals with non-zero z-component
of orbital angular momentum
These orbitals are characterized by |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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Orbitals with non-zero z-component
of orbital angular momentum
However, the behavior with respect to x and y directions
cannot be determined for these orbitals.

Alternately, one can choose the set obtained by linear

combination of orbital-pairs of given {l, |ml|}; and the
behavior with respect to x and y directions can be
studied at the cost of uncertainty in ml.

Recall the degenerate and non-degenerate eigenfunctions of

operators discussed in lecture 03.

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Linear combinations of p+1 and p-1
yields px and py orbitals.

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Linear combinations of d+1 and d-1
yields dxz and dyz orbitals.

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Linear combinations of d+2 and d-2
yields dx2-y2 and dxy orbitals.

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Orthogonal functions

The functions {fk(τ)} are said to be mutually

orthogonal if

∫fi* fjdτ =0 if i≠j; and ∫fi* fjdτ ≠0 if i=j

(^^^ apropriate limits of integration to be used)

Functions which are normalized and mutually

orthogonal are said to be orthonormal.

It can be verified that the hydrogenic orbitals are all

mutually orthogonal. (Try it yourself for a few orbitals).

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Orthogonal functions
We will now prove that the Hamiltonian eigenfunctions for
particle in 1-D box are all mutually orthogonal.
L nπ x mπx
(2/ L)∫0 sin ( )sin( )dx ; (n≠m)
L L
2 1 L πx πx
=( ) ∫0 {cos[(n−m) ]−cos [(n+ m) ]}dx
L 2 L L
L
(n−m)π x ( n+m)π x

( )
sin [ ] sin [ ]
1 L L
= − =0
L (n−m) π (n+ m) π
L L 0

Homework: Show that the Hamiltonian eigenfunctions

for 1-D harmonic oscillator corresponding to the states:
v=0 and v=1 are orthogonal.
Is this observation just a coincidence or any law governs
it?
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Hermitian operators (FYI)
●
Hermitian operator is the one, which satisfies a particular
mathematical relation, which ensures that eigenvalues of the
operator cannot be complex or imaginary. (We won't worry
about the math. Just the fact, that, eigenvalues of hermitian
operators are real, is important to us).
●
The operators corresponding to physical observables (e.g. K.E.,
P.E., Hamitonian, Angular momentum, linear momentum,
position, etc ) are all hermitian.
●
Non-degenerate eigenfunctions of hermitian operator are
always mutually orthogonal. Degenerate eigenfunctions can be
chosen to be orthogonal.
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Operators act as probes for the
corresponding observables (FYI)
The Schrödinger equation for hydrogenic atom written
is spherical coordinates, probes the orbital angular
momentum and its z-component due to which one can
obtain exact magnitude of angular momentum and
also its z-component, in addition to the energy.

If we do not probe the measurement of angular

momentum or its z-component, all that we can get is
the energy corresponding to quantum number n, and
the information that it is n2-fold degenerate.

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Operators act as probes for the
corresponding observables (FYI)
Question: Is it necessary that the hydrogenic atom
must exist in a pure-angular momentum state (that is,
a state characterized by a definite azimuthal quantum
number, l)?
The answer is, NO, unless we probe to measure the
angular momentum of the system.
Since, the orbitals corresponding to same value of
principle quantum number n, are degenerate
(eigenvalue: E n) wrt Hamiltonian, any linear
combination of the orbitals of a given shell would also
be eigenfunction of the Hamiltonian with same
eigenvalue En.

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Operators act as probes for the
corresponding observables (FYI)
From n2 orbitals (differing in l and/or ml), one can
obtain orthogonal set of n2 orbitals – hybrid orbitals:

e.g. Consider an orbital: Ψhybrid = c.ψ2s + (1-c2)1/2ψ2pz is a

hybrid orbital with n=2. The coefficients c and (1-c2)1/2
result from the orthonormality of the pure angular
momentum orbitals (2s, 2pz).

If the ratio, c2:(1-c2) = 1:n, the Ψhybrid is said to be spn

hybrid – To be discussed in detail later, in the context
of chemical bonding
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Energy levels of hydrogenic
atoms

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Ground state of hydrogenic
atom
Ground State: n = 1, l = 0, ml = 0 → 1s orbital

Ψ1,0,0 = (4π-1/2)(4/a03)1/2 e-r/a0 (independent of θ and φ →

true for all s states since Y0,0 = (4π-1/2).

All s orbitals are spherically symmetric, related to their

being states of zero angular momentum.

Probability density depends only on r; it is maximum at

r=0 (nucleus) and decays exponentially with distance r.

No nodes

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1s wavefunction and probability
density

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Radial probability distribution

Radial probability distribution function: Probability that

electron will be found between r and r+dr from the
nucleus, regardless of the angle/direction. For s
orbitals,

P(r)dr = 4πr2R2dr (for orbitals with l=0, i.e., s-orbitals)

More generally P(r) = r2R2(r); (for orbitals with l>0)

where R(r) is the radial wavefunction

For the 1s orbital (that is, for the ground state),

P(r) = (4/a03) 4πr2 e-2r/a0

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Radial probability distribution
for 1s state
Most probable distance from the nucleus = a0

How to obtain this? Set dP(r)/dr = 0 and calculate r

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Radial wavefunctions

The general form of the radial part of the

hydrogenic atom wavefunctions, obtained by
solving the radial Schrodinger equation, and
applying the necessary conditions on the solutions,
may be written
l -Zr/na0
•
Rn,l (r) α r . (Polynomial of degree n-l-1). e
•The first factor determines the behaviour at r = 0
(only l = 0 wavefunctions are nonzero at the origin)
•The second factor determines the number of radial
nodes (n-l-1)
• The third ensures that the function goes to 0 as r→∞

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Radial wavefunctions

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1s, 2s and 3s orbitals

Spherically symmetric, angular part is just a

constant
States of zero orbital angular momentum

1s
2s
3s

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p orbitals angular parts

α cos θ (pz) α sin θ sin φ (py) α sin θ cos φ (px)

l = 1, ml = 0 l = 1, ml = 1 or –1 l = 1, ml = 1 or –1
1 nodal surface 1 nodal surface (xz) 1 nodal surface (yz)
(xy)

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p orbitals boundary surfaces

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d orbitals angular parts

2 nodal planes
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