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P. 1

Term SymbolRatings:

3.5

(1)|Views: 14,160|Likes: 85Published by Cyriac Mathew

Lecture notes

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https://www.scribd.com/doc/34070262/Term-Symbol

06/02/2013

text

original

TERM SYMBOLS

Dr. Cyriac Mathew

Atomic Term Symbols

In many-electron atoms the electron configuration is rather ambiguous. For example,consider the ground state electron configuration of a carbon atom, 1s

2

2s

2

2p

2

. The two 2pelectrons could be in any of the three 2p orbitals and have any spin consistent with PauliExclusion Principle. This may give rise to several atomic energy states because of the effects of inter-electron repulsions. Therefore, we need a more detailed designation of the electronic statesof the atom. Such detailed designation of the electronic states of the atom is called

term

. Thecorresponding energy levels are represented using the

term symbol

. A term symbol tells ussomething about the angular momentum of the electrons in the atom.

Spin-orbit coupling

An electron is a charged particle, and hence its orbital angular momentum gives rise to amagnetic field just as an electric current in aloop gives rise to magnetic field in anelectromagnet. Thus an electron with an orbitalangular momentum possesses magneticmoment. The magnetic moment due to orbitalmotion is given as

le

l

,

e

is themagnetogyric ratio of the electron and

l

is theorbital angular momentum

.

An electron also hasa spin angular momentum. This intrinsicspinning motion also gives rise to magneticmoment. The spin magnetic moment is given by

2

se

s

.Where

s

is the spin angularmomentum. The spin magnetic moment is twicethe value of the spin angular momentum. Forelectrons the magnetic moment is opposite tothe angular momentum; see figure 1.Thus there are two sources for magneticmoment for the electrons. These two magneticmoments can interact and give rise to shifts inenergies of the states of the atom. Theinteraction of these two magnetic moments iscalled

spin-orbit coupling

. The strength of thecoupling, and its effect on the energy levels of the atom depend on the relative orientations of the spin and orbital magnetic moments, and henceon the relative orientations of the spin and orbital angular momenta. The total angular

NN

SS

NN

SS

High JLow J

SN

l

l

ss

l

l

ss

l

: Orbital angular momentum

l

: Orbital magnetic moments: spin angular momentum

sspin magnetic moment

:

J: Total angular momentum

Fig. 1

2

Term Symbols

Lecture notes

momentum of the electron is the vector sum of its spin and orbital momenta. Thus when the spinand orbital angular momenta are nearly parallel the total angular momentum is high; when thetwo angular momenta are opposed, the total angular momentum is low. When the total angularmomentum (J) is high, the total energy also is high (unfavourable orientation of magneticmoments), and when the total angular momentum (J) is low, the total energy also is low(favourable orientation of magnetic moments), as shown in figure 1.The probable levels that may arise as a result of vector addition of the two angular momentafrom a d

1

electron configuration is shown in fig. 2When

l

= 0 the electron is having no orbitalangular momentum and the total angularmomentum is same as that of the spin angularmomentum.

Total electronic angular momentum

When several electrons are present in anatom there are, generally, two ways in which theorbital and spin angular momenta add togetheror oppose each other.(i) Each spin may couple to its own orbitalangular momentum as in a one-electron case.This type of coupling is called

jj coupling

.(ii) All the individual orbital angular momenta(

i

l

) couple to produce a total orbital angularmomentum (

L

). It is written as vector sums:

ii

Ll

. Here the summation is over theelectrons in the atom. Similarly, the individualspin angular momenta (

i

s

) couple together to produce a total spin angular momentum (

S

).

ii

Ss

. Here also the summation is over the electrons in the atom.Now, the orbital and spin angular momenta couple to produce the total angular momentum (

J

).This type of coupling is called the

Russell-Saunders or L-S coupling

. This coupling scheme isused when the spin-orbit coupling is weak, and generally used for atoms of low atomic number(z

≤ 30).

(i) Total electronic orbital angular momentum

When several electrons are present in an atom the total orbital angular momentum isobtained by the vector addition of individual orbital angular momenta.ie. in order to find out thevalue of total orbital angular momentum we need an operator,

ˆ

L

. It can be shown that

ˆ

L

commutes with the atomic Hamiltonian,

ˆ

H

when spin-orbit coupling of individual electrons are

j

= 3/2

j

= 5/2

l

= 2

s

= 1/2

s

= 1/2

l

= 2

Fig. 2

The coupling of the spin and orbital angular momenta of a d electron(l =2) and s = ½ gives two possiblevalues of j depending on the relativeorientations of the spin and orbitalangular momenta of the electron.

3

Term Symbols

Lecture notes

neglected. Therefore we can characterize an atomic state by a quantum number

L

, so that themagnitude of the total orbital angular momentum is given as

(1)

LL

.The total orbital angular momentum (a non-negative integer) is obtained by coupling theindividual orbital angular momenta, empirically, using the Clebsch-Gordan series. If we havetwo electrons with orbital angular momenta

l

1

and

l

2

, then the total angular momentum is givenas;L =

l

1

+

l

2

,

l

1

+

l

2

–

1, ………

12

ll

The maximum value of

l

1

+

l

2

is obtained when the two orbital angular momenta are in the samedirection. The lowest value

12

ll

, is obtained when they are in opposite directions. Theintermediate values represent possible intermediate relative orientations of the two momenta.The total electronic orbital angular momentum quantum number

L

of an atom is specified by acode letter as shown below:

L

0 1 2 3 4 5 6

letter

S P D F G H IThe total orbital angular momentum is designated by a capital letter, while the individualelectronic orbital angular momentum is represented by lower case letter.

Example 1:

Let us find out the possible values of the quantum number

L

, for the states of thecarbon atom that arise from the electron configuration of 1s

2

2s

2

2p

1

3d

1

. The s-electrons have zeroorbital angular momentum and contribute nothing to the total orbital angular momentum. Nowthe p-electron has

l

= 1and designated as

l

1

and the d-electron has

l

= 2 and is designated as

l

2

.From the Clebsch-Gordan series the total orbital angular momentum quantum number rangesfrom,

L

=

l

1

+

l

2

………

12

ll

= 3 ……..

12

= 3……..1.

Therefore the possible values of

L

are 3, 2,1. The electron configuration, 1s

2

2s

2

2p

1

3d

1

, thus gives rise to P, D and F states.If more than two electrons are to be considered in a configuration then we use two series insuccession. First we couple two electrons and then we couple the third to each combined stateand so on. For eg. Let us consider the configuration 2p

1

3p

1

4p

1

. Three electrons

l

1

= 1

, l

2

= 1and

l

3

= 1. First we couple

l

1

and

l

2

and to each of the combined angular momentum we couple

l

3

.First coupling:

L

’ =

l

1

+

l

2

………

12

ll

L

’ = 1 + 1 ………1 –

1 = 2 ….. 0, hence

L’

= 2, 1, 0.Now we couple

l

3

with each value of

L’

l

3

= 1,

L’ = 2

L =

1 + 2, ……….., 1 –

2 = 3, ……. 1

L = 3, 2 ,1.

l

3

= 1,

L’ =

1

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ıt is the whole document that I need and best telling the term symbols.

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