BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 8

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 Summary (Lecture 7)

Applications of Quantum Mechanics to

Microscopic system
Quantum Mechanical Treatment of a Particle on
a Sphere (3D-Rotor)
Solution of Schrodinger Wave Equation
Eigen Values of Energy & Momentum
Wavefunctions & Physical Interpretation
Quantum Mechanical Treatment of Hydrogen Atom
(in progress)
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Hydrogen-Like Atom: Radial Solution
The acceptable solutions can be found only for integral values of a
quantum number n, 2 Zr



l
 a0
Rn ,l (r )  N n ,l   polynomialn ,l (  ) e 2 n
n
4 0  2
Normalization
a0 
me e 2
constant
polynomial in  (or r) of degree n-l-1
A term in  (or r) of degree l Associated Laguerre polynomial
Behavior at r = 0
polynomial in  (or r) of degree n-l-1
(only l = 0 wavefunctions are
:the number of radial nodes (n-l-1)
nonzero at the origin)

n = 1, 2, 3, ......
l = 0,1……(n-1)
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Hydrogenic Radial Wavefunctions
3/2
1  Z   1 2    /6
R3, 0 ( r )  1/2 

  6  2    e
9  3  a0   9 

n =3
No. of radial nodes (n-l-1) = 2
l =0

3/2
1  Z   1    /6
R3,1 ( r )  1/2

a

  4    e
3 
27  6   0  

n =3
l No. of radial nodes (n-l-1) = 1
=1
3/2
 Z 
R3, 2 ( r )  1    2e  /6
1/2  a0 
81 30   
n =3
No. of radial nodes (n-l-1) = 0
l =2
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Hydrogen-Like Atom: Wavefunction

 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
• The wavefunction ψ (r, θ, ) of the electron in the hydrogenic atom
is called an atomic orbital. An orbital is a one-electron
wavefunction.
• Electron described by a particular orbital (a state with specific set
of quantum numbers) is said to occupy that orbital.
Atomic orbitals specified by three quantum numbers n, l, and ml

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Quantum Numbers – Shell, Subshell, Orbital

• Principal quantum numbers, n Orbital angular momentum

quantum number or Azimuthal
Principal quantum number quantum number, l (Subshells)
symbolized as n is the first
Only certain discrete amounts of
quantum number of an atomic
angular momentum are allowed: l
orbital. Labels the energy levels.
l = 0 (s), 1 (p), 2 (d), 3 (f)…………….n-1
n = 1 (K), 2 (L), 3(M)……..
Orbital angular momentum L
Energy n (principal quantum no.)
Azimuthal quantum number, l
Magnetic quantum number, ml
Refers, to the direction of the angular momentum vector (around any
arbitrary axis passing through the nucleus): Space Quantization
One of the spatial components of Angular momentum, Lz ml
Each subshell contains 2l+1 individual orbitals.

l = 0 & ml = 0: s-orbital; l = 1 & ml = +1, 0, -1 : three p-orbitals

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Atomic orbital

Atomic orbital is a Associated Spherical

one-electron Laguerre harmonics
= polynomials
wavefunction specified with
defined by 3 multiplied by an l and ml
quantum numbers exponential, and
(n, l, ml) characterized by n
and l
Atomic Orbital represented by : nlml
n: numerals (1,2,…);
l: (letters) 0 = s; 1= p; 2 = d; 3 = f….
ml = +l………-l
Eg.: if n=3 and l = 2 and ml (5 values) = 2,1,0,-1,-2
How many orbitals for a given n ? n2
→ 3d2, 3d1, 3d0 , 3d-1 , 3d-2 orbitals
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Shells and subshells In hydrogenic atoms, all orbitals in the same shell have the
same energy (characterized by n). NB: In many-electron
ml ≤ |l |
atoms, we’ll see that the subshells have different energies.
ml
l

Number of orbitals
with different ml
l ≤ (n-1)

n= 1 2 3 4
K L M N

l= 0 1 2 3
s p d f
n
How many orbitals for a given n ? n2 8
Hydrogen-Like Atom: 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.
In hydrogenic atoms, all orbitals in the same shell
have the same energy (characterized by n). NB: In
many-electron atoms, we’ll see that the subshells have n=1, Z=1
different energies.
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/n21)
= h

-
 = R[(1/n12) – (1/n22)]

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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 wavefunction and probability density

Radial wavefunction

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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
P   *d 1s = (1/a31/2 e-r/a
a

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

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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 = 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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 Hydrogenic Wavefunctions
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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