Cornelius T.

Moynihan
I Rationalization of the A l = +1 Selection
-
California State College
at 10s Angeles
LOS Angeles 90032 I Rule for Rotational Transitions

It is frequently necessary in introduc-

tory courses to present quantum mechanical results
IUJ = ,
h -
+
~ J ( J 1)
without deriving them in a rigorous fashion. Occasion- where wJ is the angular velocity and I the moment of
ally, however, there exists a simple classical physical inertia. Since wJ = Z a u ~ then
, the rotational frequency
analog of the quantum mechanical system that allows is
one to rationalize the quantum mechanical result in ----
familiar terms and to satisfy, at least partially, the VJ = pih +
~ J ( J 1) = +
B ~ ~ J ( 1J) (2)
student's curiosity as to the origin of the result. where B = rotational constant = (h/Sa21). Similarly,
A case in point is the set of selection rules for the pure
rotational energy transitions observed in the far in-
the rotational frequency in the ( J njthstateis +
frared or microwave spectrum of a linear molecule. VJ+. = Bd4(J + n ) ( J + n + 1) (3)
The gross selection rule for such transitions states that The rotational energy in the J t h level is
the molecule will exhibit a pure rotational absorption
spectrum only if the molecule possesses a permanent EJ = BhJ(J + 1)
dipole moment. As most textbooks note, this rule is Hence the energy change for the J + J + n transition is
easily rationalized in terms of an interaction between EJ+, - Er = huphaen=
the oscillating electrical field generated by the rotating
dipole and the oscillating electrical field of the light
Bh(J + n ) ( J + n + 1) - B W ( J + 1)
wave or photon inducing the transition.' and
The second selection rule for pure rotational transi-
tions is 4J = * I , where J is the rotational quantum
u.l,,k. = Bn(2J +n+ 1) = Bdnz(2J +n + 1)2 (4)
number. Many elementary texts simply state this rule Substituting eqns. (Z), (3), and (4) into condition 1 and
without proof, hut in fact it can he rationalized by a dividing through by B gives
slight extension of the same physical model used to
explain the first selection rule. I n particular, if one
d4J(J + 1 ) < dn2(2J + n + I)* <
imagines that the rotating molecular dipole increases its d4(5 + n ) ( J + n + 1) (5)
rotational speed and hence its rotational energy by a Substitution of a few trial values of n shows immediately
coupling between the alternating electrical field of the that the only positive integer value of n for which con-
rotating dipole and the alternating electrical field of the dition 5 is satisfied is n = 1, and hence 4J = $1 for
light wave, the coupling process will clearly be most the rotational absorption spectrum. The reverse con-
efficient when the two fields are oscillating in phase with dition, 4J = - 1, applies in the case of photon emission,
the same frequency. As soon as the molecule begins to
absorb energy from the light wave, however, its rota-
so that the overall selection rule is A J = 1. *
By way of final comment, it is worth noting that
tional speed will increase, the two oscillating fields will arguments similar to those presented above can he used
no longer have the same frequency, and hence they will t o rationalize the 4 v = *l selection rule for the har-
no longer be in phase. The most reasonable com- monic oscillator or the Am, = *1 selection rule for
promise would seem to be that the frequency of the magnetic dipole transitions in nmr spectroscopy. Most
light wave should be intermediate between the rota- texts point out that for allowed energy transitions in
tional frequency of the molecule in its initial state and these cases the photon frequency matches respectively
the rotational frequency in the final state. That is the fundamental vibration frequency of the harmonic
v~ < va.t. < vr+" (1) oscillator or the Larmor precession frequency of the
nuclear magnetic dipole. If one reverses these argu-
where vr is the frequency of molecular rotation in the ments, one a rationalization of the respective
initial Jth state, V J + . is the rotational frequency in the selection rules. ~h~~~ last two cases are, of course,
+
final (J n) state, and vshobn is 'he frequency of the light simpler than the case of the rotating molecule, since the
wave inducing the transition. If we accept condition 1 frequency of the alternating field associated with the
as a valid requirement for photon absorption, it is not molecular system is independent of the energy level of
difficult to show that condition 1 is satisfied only for the system,
n = 1, and hence that the selection rule for pure rota-
tional absorption spectra is 4J = + l . The proof is as
A lucid presentation of this, as well as a helpful illustration for
follows. understanding the discussion to follow, is given in BARROW, G. M.,
The angular momentum of a rigid rotating linear "The Strnctme of Molecules," W. A. Benjamin, Inc., New
molecule in the J t h energy level is York, 1964, pp. 46-48.

Volume 46, Number 7, July 1969 / 431