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Indian Institute of Technology, Guwahati: CH101 Class 11 Physical Chemistry

1) The document describes the quantum numbers (n, l, ml, ms) that define the state of an electron in hydrogenic atoms. 2) It provides equations for the energy levels of electrons in hydrogenic atoms and how the energy depends on the principal quantum number n. 3) It gives the wavefunctions for 1s, 2p, and 3d orbitals and describes their shapes and orientations in space.

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Mihir Kumar Mech
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39 views

Indian Institute of Technology, Guwahati: CH101 Class 11 Physical Chemistry

1) The document describes the quantum numbers (n, l, ml, ms) that define the state of an electron in hydrogenic atoms. 2) It provides equations for the energy levels of electrons in hydrogenic atoms and how the energy depends on the principal quantum number n. 3) It gives the wavefunctions for 1s, 2p, and 3d orbitals and describes their shapes and orientations in space.

Uploaded by

Mihir Kumar Mech
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Indian Institute of Technology, Guwahati

Guwahati, INDIA 781 039


Department of Chemistry

Date: 08 October 2014


CH101
Class 11; Physical Chemistry

Hydrogenic Atoms
Principal quantum number: n ; takes the values of 1, 2, 3,
n decides the values of energy

Z 2 e 4
En
32 2 02 2 n 2
The angular solutions provide the other two quantum numbers
l is the azimuthal quantum number or orbital angular momentum quantum number
An electron in an orbital with quantum number ml has the angular momentum of
magnitude

l (l 1)

with l = 0, 1, 2, .n- l. Note how the principal quantum

number n decides the values of l.


An electron in an orbital with quantum number ml has a z-component of angular
momentum

m ; with ml = 0, 1, 2, 3, ..l.
l

Note how the quantum number l

decides the values of ml.


In order to define a state of electron in hydrogenic atoms one needs to consider also the
spin of electron. Electron posses an intrinsic angular momentum that is described by two
quantum numbers s and ms.
The value of s is fixed at for an electron.
ms can be either + or .
The state of an electron in hydrogenic atoms is defined by n, l, ml and ms.

The energy levels of an electron in hydrogenic atoms are defined by

Z 2 e 4
2
Thus En Z and hence the ground state of He+ is four times
En
2 2 2 2
32 0 n
deeper than that in H.
The energy states here are referred to the bound states of the atoms in which the energy
of the electron is lower in any of these states than if the electron and nucleus were
infinitely separated.
From the spectroscopic results of hydrogen atom we have the Rydberg constant

1 1
e
E E R ( ) hcR
n n
32
4

n1

n2

Thus RH

Hence

H e4
mee 4
and
In
general,
R

8 02 h3c
8 02 h3c

R
H

Do it now:
Calculate RH from the following fundamental constants
Mass of electron, me=9.109 38 x 10-31 kg
Charge of electron, e=1.602 176 x 10-19 C
0 = 8.854 19 x 10-12 J-1 C2 m-1
h = 6.626 08 x 10-34 J s
c = 2.997 924 58 x 108 m s-1
Answer: 1.097 37 x 105 cm-1.

Atomic Orbitals:
Consider the ground state orbital of the hydrogenic atom
n = 1, l = 0, ml = 0

Z
R 2
a

3/ 2

/ 2

; where

2Zr
a

and

1
4

( , )
l , ml

The wavefunction, for Z = 1, can then be written as:

1
e
(a )
3

r / a0

1/ 2

; The wavefunction is independent of angle and has the same

for all angles at a particular value of r.

Radial distribution function:

is the probability density of finding an electron in any region.

e
2

For the electron in the ground state

2 Zr / a 0

Now consider the probability of finding the electron anywhere on a spherical shell with
thickness dr and radius r.
The volume of the shell is 4r2dr
The probability that the electron will be found anywhere between the distance r and

4r dr P(r )dr ; where P(r ) 4r


2

r+dr and in the shell is

The above expression is Radial Probability and is valid for electrons in orbitals that are
spherically symmetric.
When the orbital is not spherically symmetric then,

P(r )dr R(r ) Y ( , ) r dr sin dd

r R(r ) dr
2

Y ( , ) sin dd r R(r ) dr
2

The last equation follows that the spherical harmonics are normalized.

Hence the expression for probability density of non-spherically symmetric


wavefunctions is

P( r ) r R( r )
2

For a 1s orbital of hydrogenic atoms,


3

4Z
P(r )
re
a
2

2 Zr / a 0

The wavefunction for a 2p orbital with ml=0 is


Z

p0 R2,1 (r )Y1,0 ( , )
4(2 )1 / 2 a0
r cosf (r )
1

5/ 2

r cose Zr / 2a0

p z zf (r )

This orbital is called 2pz orbital and has a node in the x-y plane
The wavefunctions of 2p orbitals with ml=1 have the following form.

1
R (r )Y ( , )
8( )
p 1

1, 1

2 ,1

1/ 2

re

5/ 2

Zr / 2 a 0

sin e

The functions above correspond to a -dependent function for a particle with angular
momentum either clockwise or anti-clockwise around the Z-axis.

They have zero

amplitude when =0 and 180o and maximum amplitude at 900 which is in xy-plane. The
linear combination of the above functions would generate real functions.

1
( p p ) r sin cosf (r ) xf (r )
2
i

( p p ) r sin sin f (r ) yf (r )
2

px

py

1/ 2

1/ 2

These linear combinations are standing waves with no net orbital angular momentum
around the z-axis, as they are superposition of states with equal and opposite values of
angular ml. The px orbital has the same shape as the pz orbital but directed along the x4

axis. Similarly the py orbital has the same shape as the pz orbital but directed along the yaxis.

d-orbitals
When n = 3, l can be 0, 1 or 2. The shell consists of one 3s orbital, three 2p orbitals and
five 3d orbitals. The five d orbitals have ml = +2, +1, 0, -1, -2 and correspond to five
different angular momenta around the z-axis (but the magnitude of the momentum is the
same as l=2).

d xyf (r ) ; d yzf (r )
xy

yz

d zxf (r )
zx

1
( x y ) f (r )
2
1
d
(3z r ) f (r )
2 3
d

x y
2

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