BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 7

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 Summary (Lecture 6)

Hydrogenic Atoms: Spherically symmetric Potential

2  
  2
2  1  1  2
1     
Hˆ      2 2   sin     V (r )
2    r 2
r  r r  sin    2
sin        

Hˆ  (r , ,  )  E (r , ,  )
 n,l ,m (r , ,  )  Rn,l (r )l ,m    m    Rn,l (r ) Yl ,m ( ,  )
l l l l

iml
e
Yl,ml( , ϕ)  N l ,ml polynomiall ,ml ( ).
2 1/ 2

Spherical Harmonics: Associated Legendre Polynomials

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 Summary (Lecture 6)


l
 2 Zr
Rn ,l (r )  N n,l   polynomialn ,l (  ) e 2n

n a0
Radial Wave function: Associated Laguerre Polynomials

 n ,l ,m (r ,  ,  )  Rn ,l (r ) Yl ,m ( ,  )
l l
 im

l
 e
 n,l ,ml (r , ,  )  N n,l ,ml .  . polynomialn,l (  ). e 2 n . polynomiall ,ml ( ).
n 2
n = 1,2,….; l = 0,1,…….(n-1); ml = -l,…….+l
Energy Angular momentum z-component of AM.
No .of Radial nodes are (n-l-1) and no. of angular nodes are (l).
The wavefunction ψ (r, θ, ) of the electron in the hydrogenic atom
is called an atomic orbital. An orbital is a one-electron
wavefunction.
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 1s – Wave function
3/2
 Z 
R1, 0 (r )  2  e  /2
a 
 0 

The wavefunction has maximum value at nucleus. (r = 0);

Nuclear-electron interactions are through s orbital. 

Hyperfine Interactions.

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Hydrogenic Atoms:
Eigen Value: Energy
The energy levels are
En = e4Z2/32ħn2
n = 1,2,3,….
(Energy depends only on n)
n=2, Z=1
En = - hcRZ2/n2
hcR = e4/32ħ
 = mmN/(m+mN)
Constant R is numerically same
as Rydberg contant, RH when
mN is set equal to the mass of proton.
n=1, Z=1
Ground state is stable than infinitely
separated electron and nucleus.
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Energy levels & Ionization energies

En = hcRZ2/n2
 The energies given by the formula are negative, they correspond to a bound
state of the electron.
The zero energy, reference level (n = ∞) for the energy, corresponds to a
situation where the electron is not bound.
 The positive energies correspond to unbound states of the electron. The
wavefunction describing such an electron is also solution of the SE, and it is the
wavefunction of a free electron. The energy of the unbound electron are not
quantized and form the continuum states of the atom.

The ionization energy I, of an atom is the minimum energy required to

remove an electron from the atom that is in its ground state (the state of lowest
energy of the atom).
e.g: For H, there is one electron. The atom is in its ground state when the
electron is in the state characterized by n=1.
I= -En=1 = hcRH = 2.179 10-18J= 13.6 eV
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Principal quantum numbers, n: Energy Levels

Spectroscopy measures the

changes in energy between two
states.

E = hcR/n22 – (- hcR/n12)
= h

-
 = R[(1/n12) – (1/n22)]

Excited state to Ground state

transition is called Relaxation; This
can be radiative or non-radiative.

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Ground state of hydrogenic atom
Ground State: n = 1, l = 0, ml = 0  1s orbital
• Ψ1,0,0 = (4-1/2 (4/a03)1/2 e-r/a0 = (1/a031/2 e-r/a0
(independent of  and , true of all s states since Y00 = (4-1/2 ).
• All s orbitals are
spherically symmetrical, related to their being
states of zero angular momentum.

• Probability density depends only on r

Maximum at r = 0, the nucleus: Most probable point at which electron
will be found is at nucleus.
• Decays exponentially with distance r
• No nodes
• Function above is normalized.

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1s wave function and probability density

Radial wave function

90% electron probability

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Spherical polar  Cartesian

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Volume Element in Spherical Polar Coordinates

Therefore, dV = dτ = (dr) (r dθ) (rsinθ d𝝓)

d  r 2 dr sin dd
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1s wavefunction and probability density
What is the probability that an electron in the 1s orbital of hydrogen
will be within a radius of 2Å from the nucleus?
b
3/2
P    d *  Z
2

  1 
e  /2 
1/2

a  
a
 0   4 
For hydrogen atom, this becomes the three dimensional expression
2 A 2
P  
0 0 0
 *r 2 dr sin dd
2 
d  r 2 dr sin dd
2A
1
 d. sin d .  r e
2 2r / a
 3 dr
a 0 0 0

P = 0.981 Note: ‘a’ has to be in Å

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 1s – Wavefunction

• For all values of ϕ & , there is a very small volume near the
nucleus and probability of electron existing in such a small volume
should be small.

• Electron probability should not be considered along a straight line

out from nucleus.
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 1s – radial distribution function

Volume of spherical shell (shaded) = 4r2dr

• Electron probability should be considered on a spherical surface

around the nucleus.
• Probability that the electron will be found in this spherical shell is
=(Prob. density at the radius r) x (volume of spherical shell)
= ψ2 4r2 dr = P(r)dr ; P(r) = 4r2ψ2
Radial distribution function, P(r): gives the probability of finding the
electron in a spherical shell of thickness dr (between r and r+dr) at the
radius r from the nucleus, regardless of the angle/direction.
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1s – radial distribution function Plot
For the 1s orbital, Ψ1s = (1/a031/2 e-r/a0
Therefore, P(r) = 4r2 Ψ21s

= 4r2 [(1/a031/2 e-r/a0]2

P(r) = (4/a03) r2 e-2r/a0.

P(r) = 0 at r = 0

P(r)  0 as r  
• The probability starts at zero, increases to a maximum value, then decreases
toward zero as the radius gets larger and larger.
•The most probable radius is the radius at which P(r) is maximum.
At most probable radius, dP(r)/dr = 0
• For a 1s orbital in hydrogen, P(r) is maximum at r = a0 (Bohr radius).
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2s –radial distribution function Plot
• Spherically symmetric, angular part is just a constant (states of zero
orbital angular momentum).
3/2
1  Z   1    /4
R2, 0 (r )  1/2 

  2   e
2  2   a0   2 
ρ = 2Zr/ao

For calculating the position of radial node:

At radial node, (2 – ρ /2) = 0. Therefore, the radial node is at r = 2ao/Z

P(r) = 4r2 Ψ22s

At most probable radius, dP(r)/dr = 0

For 2s orbital in H-atom, most probable radius is 5.2ao
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 Radial Wavefunction
Ψ2,0,0 = (1/ √(32π)) (Z/a)3/2 (2 - Zr/a) e-Zr/2a

Ψ1,0,0 = (1/ √π) (Z/a)3/2 e-Zr/a Ψ3,0,0 = 1/(81√(3π)) (Z/a)3/2 (27 - 18(Zr/a) + 2(Zr/a)2) e-Zr/3a

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Radial Distribution Plot (P(r) vs r)

P(r) = Radial
Distribution
Function

Locate the
maxima for
finding the “most
probable radius”

dP(r)/dr = 0
Find rmax.

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Most probable and average radius
• For most probable radius solve for “r” in

d P(r)/dr = 0 or d(4πr2 Ψ2)/dr =0

rmp = ao = 0.529Å (1s)

• For average radius find the expectation value

=  
*
<r> r d

ravg = (3/2) (ao)/Z = (3/2) ao (1s of Hydrgen)

Average radius is higher than most probable radius as a

substantial portion of electron distribution is after rmp.
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Radial distribution function P(r) for orbitals
that are not spherically symmetrical:
• Probability of finding the electron in an
infinitesimal volume element d located at a
distance between r and r+dr from nucleus, with its
angular coordinates having values between  and
+d and between  and + d is

ψ ψ* d = [Rn,l(r)]2 [Yl,ml(,)]2r2 dr sin dd

• The Probability of finding the electron between r and r+dr from the
nucleus, regardless of angle ( and ) can be obtained by integrating over 
and  is
 2

 
0 0
Rn,l(r)]2 [Yl,ml(,)]2 r2 dr sin dd

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Radial distribution function P(r) for orbitals
that are not spherically symmetrical:
 2
Probability = P(r)dr = r2 Rn,l(r)]2 dr  
0 0
[Yl,ml(,)]2 sin dd

Integral of [Yl,ml(,)]2 can be normalized to unity (1)

Therefore, Probability, P(r)dr = r2 [Rn,l(r)]2 dr

Radial distribution function, P(r) = r2 [Rn,l(r)]2

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 Radial wavefunction & Radial
Distribution Plots (P(r) or r2R2 vs. r)

2p 3p 3d

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2pz Orbital : Wavefunction n=2; l=1; ml = 0
1/2
 2,1, 0  R2,1 (r ) Y1, 0 ( ,  ) 
3/2
 Z   3 
1    e  /4  4  cos 
1/2 a 
4  6  0   
n = 2, l = 1, ml = 0
No. of radial nodes (n-l-1) = 0 In spherical polar coordinate‘s z = r cos 
No. of nodes (n-1) = 1
• These orbitals have maximum probability density oriented along z-
direction.
• At r = 0, wavefunction is zero.
• The wavefunction is also zero everywhere on the x-y plane
(cos  = 0 when  = 90o). Nodal plane (1, xy-plane)
The power (l) on r (or ρ) or power of  term = No of
angular nodes =1
• These represents atomic states for which energy and
magnitude of the orbital angular momentum can be exactly
known.
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2p Orbitals : Wavefunction n=2; l=1; ml = ±1
 1

 2 p  R2,1 (r ) Y1,1 ( ,  )
1
1 
 Z 

3/2
  3
 e  /4    sin e 
2
i 

4  6
1/2  a0 
    8  
 
3/2  1

 2 p  R2,1 (r ) Y1, 1 ( ,  ) 1 
 Z 

e   /4   3  2
 i 
1
  8  sin e 
1/2  a0    
4  6    

n = 2, l = 1, ml = 1 or -1 No. of radial nodes (n-l-1) = 0 No. of nodes (n-1) = 1

• These wavefunction contains a imaginary exponential part, thus the
overall wavefunction is a complex function.

• The maximum probability density of these orbitals is oriented off-the

z-axis, but along which direction(s), cannot be determined.

• These orbitals do not provide the information of properties that are

strongly responsive to orientation in three dimensional space.
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2p Orbitals : Wavefunction n=2; l=1; ml = ±1
3/2  1

 2 p  R2,1 (r ) Y1,1 ( ,  ) 1  Z


 e   /4 

3 

2
sin e i 
1
4  6
1/2 a   8 
 0    
 
3/2  1

   i 
 2 p  R2,1 (r ) Y1, 1 ( ,  )  Z  3 2
1    e  /4    sin e 
1
4  6
1/2  a0    8  
   

• Real wavefunctions could be defined by linear combinations of complex

wavefunctions such that now the orientation of the maximum probability
density could be identified. 5
 zr
 1   z  2
 2 p1  2 p1   
   e 2 a0
r sin  cos    2 p
 16   a0  x

1 nodal surface (yz plane) x= r sin  cos ϕ

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 zr
 2 p  2 p  1   z 2
1 1
    e 2 a0
r sin  sin    2 py
i  16   a0 
1 nodal surface (xz plane) Y = r sin  sin ϕ
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2p orbitals – boundary surfaces

 2p x and  2p y

These non-imaginary wavefunctions

No. of Radial Node: n-l-1 are not the eigenfunctions of Lz
No. of angular Node: l (ml is uncertain in terms of sign).
Total no. of nodes: (n-1) but are still the eigenfunctions of
energy and total angular momentum.
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