The Chemistry Maths Book, Second Edition

(Grace) #1

424 Chapter 15Orthogonal expansions. Fourier analysis


This analysis of the potential is important for the description of the electrostatic


interaction of charge distributions, for example in the theory of intermolecular forces.


The quantities


(15.29)


in (15.28) are called the electric multipole momentsof order lof the charge


distribution (strictly,Q


l

is the component of the multipole in the direction OP, see


Chapter 16). The expansion (15.28) is called the multipole expansionof the potential.


The first few moments are


total charge


dipole moment (15.30)


quadrupole moment


EXAMPLE 15.4The field of a dipole


For the system shown in Figure 15.3 of two unlike


charges+qand−qseparated by distance r:


1.Q


0

1 = 1 +q 1 − 1 q 1 = 10


and the total charge is zero.






whereμ 1 = 1 qris the (scalar) dipole moment of the pair of charges, andμ 1 cos 1 θis


the component of the dipole moment in the direction OP.






and, becauseP


l

(cos 1 θ)is an even function ofcos 1 θ, every even-order multipole


moment is zero.


Qq


r


q


r


2

2

2

2

2


1


2


31


2


1


2


= 3








⋅−−








(cos )θ ⋅ (coos ( ) )


2

π+−=θ 10


Qqr qr qr


1

1


2


1


2


=− +==cosθθθθcos(π ) cos μcos


Qqr


i

N

2 ii i

1

22

1


2


=− 31


=


(cos )θ


Qqr


i

N

1 ii i

1

=


=


cosθ


Qq


i

N

0 i

1

=


=


QqrP


l

i

ii

l

li

=



(cos )θ


...............................................................................................................................................................................................................................................

.

...

...

...

...

..

...

...

...

...

..

...

...

...

...

...

..

...

...

...

..

...

...

...

...

..

...

...

...

...

...

..

...

...

...

..

...

...

...

...

..

...

...

...

..

...

...

...

...

...

..

...

..













o


+q


−q


p


R


r/ 2


r/ 2


..

..

...

..

...

...

....

....

θ


Figure 15.3

Free download pdf