point group t o which t he at om or molecule belongs, t hen t he int egral's value is (in general) not

zero and t he t ransit ion is allowed. Ot herwise, t he t ransit ion is "forbidden".

The t ransit ion moment int egral is zero if t he transition moment function, is ant i-
symmet ric or odd, i.e. holds. The symmet ry of t he t ransit ion moment
funct ion is t he direct product of t he parit ies of it s t hree component s. The symmet ry
charact erist ics of each component can be obt ained from st andard charact er t ables. Rules for
obt aining t he symmet ries of a direct product can be found in t ext s on charact er t ables.[2]

Symmet ry charact erist ics of t ransit ion moment operat or[2]

Transit ion t ype μ t ransforms as Cont ext

Elect ric dipole x, y, z Opt ical spect ra

Elect ric quadrupole x2, y2, z2, xy, xz, yz Const raint x2 + y2 + z2 = 0

Elect ric polarizabilit y x2, y2, z2, xy, xz, yz Raman spect ra

Magnet ic dipole R x, R y , R z Opt ical spect ra (weak)

Examples

Electronic spectra

The Laport e rule is a select ion rule formally st at ed as follows: In a cent rosymmet ric
environment , t ransit ions bet ween like at omic orbit als such as s- s, p- p, d- d, or f- f, t ransit ions are
forbidden. The Laport e rule (law) applies t o elect ric dipole t ransit ions, so t he operat or has u
symmet ry (meaning ungerade, odd).[3] p orbit als also have u symmet ry, so t he symmet ry of t he
t ransit ion moment funct ion is given by t he t riple product u×u×u, which has u symmet ry. The
t ransit ions are t herefore forbidden. Likewise, d orbit als have g symmet ry (meaning gerade, even),
so t he t riple product g×u×g also has u symmet ry and t he t ransit ion is forbidden.[4]

The wave funct ion of a single elect ron is t he product of a space-dependent wave funct ion and a
spin wave funct ion. Spin is direct ional and can be said t o have odd parit y. It follows t hat
t ransit ions in which t he spin "direct ion" changes are forbidden. In formal t erms, only st at es wit h
t he same t ot al spin quant um number are "spin-allowed".[5] In cryst al field t heory, d- d t ransit ions
t hat are spin-forbidden are much weaker t han spin-allowed t ransit ions. Bot h can be observed, in
spit e of t he Laport e rule, because t he act ual t ransit ions are coupled t o vibrat ions t hat are ant i-
symmet ric and have t he same symmet ry as t he dipole moment operat or.[6]
Vibrational spectra

In vibrat ional spect roscopy, t ransit ions are observed bet ween different vibrat ional st at es. In a
fundament al vibrat ion, t he molecule is excit ed from it s ground st at e (v = 0) t o t he first excit ed
st at e (v = 1). The symmet ry of t he ground-st at e wave funct ion is t he same as t hat of t he
molecule. It is, t herefore, a basis for t he t ot ally symmet ric represent at ion in t he point group of
t he molecule. It follows t hat , for a vibrat ional t ransit ion t o be allowed, t he symmet ry of t he
excit ed st at e wave funct ion must be t he same as t he symmet ry of t he t ransit ion moment
operat or.[7]

In infrared spect roscopy, t he t ransit ion moment operat or t ransforms as eit her x and/or y and/or
z. The excit ed st at e wave funct ion must also t ransform as at least one of t hese vect ors. In
Raman spect roscopy, t he operat or t ransforms as one of t he second-order t erms in t he right -
most column of t he charact er t able, below.[2]

Charact er t able for t he Td point group

E 8 C3 3 C2 6 S4 6 σd

A1 1 1 1 1 1 x2 + y2 + z2

A2 1 1 1 -1 -1

E 2 -1 2 0 0 (2 z2 - x2 - y2,x2 - y2)

T1 3 0 -1 1 -1 (Rx, Ry, Rz)

T2 3 0 -1 -1 1 (x, y, z) (xy, xz, yz)

The molecule met hane, CH4, may be used as an example t o illust rat e t he applicat ion of t hese
principles. The molecule is t et rahedral and has Td symmet ry. The vibrat ions of met hane span t he
represent at ions A1 + E + 2T 2.[8] Examinat ion of t he charact er t able shows t hat all four vibrat ions
are Raman-act ive, but only t he T 2 vibrat ions can be seen in t he infrared spect rum.[9]

In t he harmonic approximat ion, it can be shown t hat overt ones are forbidden in bot h infrared and
Raman spect ra. However, when anharmonicit y is t aken int o account , t he t ransit ions are weakly
allowed.[10]

In Raman and infrared spect roscopy, t he select ion rules predict cert ain vibrat ional modes t o have
zero int ensit ies in t he Raman and/or t he IR.[11] Displacement s from t he ideal st ruct ure can result
in relaxat ion of t he select ion rules and appearance of t hese unexpect ed phonon modes in t he
spect ra. Therefore, t he appearance of new modes in t he spect ra can be a useful indicat or of
symmet ry breakdown.[12][13]
Rotational spectra

The select ion rule for rot at ional t ransit ions, derived from t he symmet ries of t he rot at ional wave
funct ions in a rigid rot or, is ΔJ = ±1, where J is a rot at ional quant um number.[14]

Coupled transitions

The infrared spectrum of HCl gas

There are many t ypes of coupled t ransit ion such as are observed in vibrat ion-rot at ion spect ra.
The excit ed-st at e wave funct ion is t he product of t wo wave funct ions such as vibrat ional and
rot at ional. The general principle is t hat t he symmet ry of t he excit ed st at e is obt ained as t he
direct product of t he symmet ries of t he component wave funct ions.[15] In rovibronic t ransit ions,
t he excit ed st at es involve t hree wave funct ions.

The infrared spect rum of hydrogen chloride gas shows rot at ional fine st ruct ure superimposed on
t he vibrat ional spect rum. This is t ypical of t he infrared spect ra of het eronuclear diat omic
molecules. It shows t he so-called P and R branches. The Q branch, locat ed at t he vibrat ion
frequency, is absent . Symmet ric t op molecules display t he Q branch. This follows from t he
applicat ion of select ion rules.[16]

Resonance Raman spect roscopy involves a kind of vibronic coupling. It result s in much-increased
int ensit y of fundament al and overt one t ransit ions as t he vibrat ions "st eal" int ensit y from an
allowed elect ronic t ransit ion.[17] In spit e of appearances, t he select ion rules are t he same as in
Raman spect roscopy.[18]
Angular momentum
See also angular momentum coupling

In general, elect ric (charge) radiat ion or magnet ic (current , magnet ic moment ) radiat ion can be
classified int o mult ipoles Eλ (elect ric) or Mλ (magnet ic) of order 2λ, e.g., E1 for elect ric dipole, E2
for quadrupole, or E3 for oct upole. In t ransit ions where t he change in angular moment um
bet ween t he init ial and final st at es makes several mult ipole radiat ions possible, usually t he
lowest -order mult ipoles are overwhelmingly more likely, and dominat e t he t ransit ion.[19]

The emit t ed part icle carries away an angular moment um λ, which for t he phot on must be at
least 1, since it is a vect or part icle (i.e., it has JP = 1− ). Thus, t here is no radiat ion from E0 (elect ric
monopoles) or M0 (magnet ic monopoles, which do not seem t o exist ).

Since t he t ot al angular moment um has t o be conserved during t he t ransit ion, we have t hat

where and it s z-project ion is given by and where and

are, respect ively, t he init ial and final angular moment a of t he at om. The corresponding
quant um numbers λ and μ (z-axis angular moment um) must sat isfy

and

Parit y is also preserved. For elect ric mult ipole t ransit ions

while for magnet ic mult ipoles

Thus, parit y does not change for E-even or M-odd mult ipoles, while it changes for E-odd or M-
even mult ipoles.

These considerat ions generat e different set s of t ransit ions rules depending on t he mult ipole
order and t ype. The expression forbidden transitions is oft en used, but t his does not mean t hat
t hese t ransit ions cannot occur, only t hat t hey are electric-dipole-forbidden. These t ransit ions are
perfect ly possible; t hey merely occur at a lower rat e. If t he rat e for an E1 t ransit ion is non-zero,
t he t ransit ion is said t o be permit t ed; if it is zero, t hen M1, E2, et c. t ransit ions can st ill produce
radiat ion, albeit wit h much lower t ransit ions rat es. These are t he so-called "forbidden" t ransit ions.
The t ransit ion rat e decreases by a fact or of about 1000 from one mult ipole t o t he next one, so
t he lowest mult ipole t ransit ions are most likely t o occur.[20]

Semi-forbidden t ransit ions (result ing in so-called int ercombinat ion lines) are elect ric dipole (E1)
t ransit ions for which t he select ion rule t hat t he spin does not change is violat ed. This is a result
of t he failure of LS coupling.

Summary t able

is t he t ot al angular moment um, is t he Azimut hal quant um number, is t he

Spin quant um number, and
is t he secondary t ot al angular moment um quant um number.
Which t ransit ions are allowed is based on t he Hydrogen-like at om. The symbol is used t o
indicat e a forbidden t ransit ion.
 Elect ric Magnet ic Elect ric Magnet ic Elect ric Magnet ic
Allowed
dipole dipole quadrupole quadrupole oct upole oct upole
t ransit ions
(E1) (M1) (E2) (M2) (E3) (M3)

(1)
Rigorous
rules (2)

(3)

No
One None or one One One
elect ron One elect ron
elect ron elect ron elect ron elect ron
jump
jump

(4) jump jump jump jump

LS coupling
If
If If
If

(5)

If If
If

If

If

Int ermediat e

(6)
coupling

In hyperfine st ruct ure, t he t ot al angular moment um of t he at om is where is t he

nuclear spin angular moment um and is t he t ot al angular moment um of t he elect ron(s). Since
has a similar mat hemat ical form as it obeys a select ion rule t able
similar t o t he t able above.

Surface

In surface vibrat ional spect roscopy, t he surface selection rule is applied t o ident ify t he peaks
observed in vibrat ional spect ra. When a molecule is adsorbed on a subst rat e, t he molecule
induces opposit e image charges in t he subst rat e. The dipole moment of t he molecule and t he
image charges perpendicular t o t he surface reinforce each ot her. In cont rast , t he dipole
moment s of t he molecule and t he image charges parallel t o t he surface cancel out . Therefore,
only molecular vibrat ional peaks giving rise t o a dynamic dipole moment perpendicular t o t he
surface will be observed in t he vibrat ional spect rum.

See also

Superselect ion rule

Spin forbidden react ions

Notes

1. Harris & Bertolucci, p. 130

2. Salthouse, J.A.; Ware, M.J. (1972). Point Group Character Tables and Related Data. Cambridge
University Press. ISBN 0-521-08139-4.

3. Anything with u (German ungerade) symmetry is antisymmetric with respect to the centre of
symmetry. g (German gerade) signifies symmetric with respect to the centre of symmetry. If the
transition moment function has u symmetry, the positive and negative parts will be equal to each
other, so the integral has a value of zero.

4. Harris & Berolucci, p. 330

5. Harris & Berolucci, p. 336

6. Cotton Section 9.6, Selection rules and polarizations

7. Cotton, Section 10.6 Selection rules for fundamental vibrational transitions

8. Cotton, Chapter 10 Molecular Vibrations

9. Cotton p. 327

10. Califano, S. (1976). Vibrational states. Wiley. ISBN 0-471-12996-8. Chapter 9, Anharmonicity

11. Fateley, W. G., Neil T. McDevitt, and Freeman F. Bentley. "Infrared and Raman selection rules for lattice
vibrations: the correlation method." Applied Spectroscopy 25.2 (1971): 155-173.

12. Arenas, D. J., et al. "Raman study of phonon modes in bismuth pyrochlores." Physical Review B 82.21
(2010): 214302. || DOI:https://doi.org/10.1103/PhysRevB.82.214302

13. Zhao, Yanyuan, et al. "Phonons in Bi 2 S 3 nanostructures: Raman scattering and first-principles
studies." Physical Review B 84.20 (2011): 205330. ||
DOI:https://doi.org/10.1103/PhysRevB.84.205330
 14. Kroto, H.W. (1992). Molecular Rotation Spectra. new York: Dover. ISBN 0-486-49540-X.

15. Harris & Berolucci, p. 339

16. Harris & Berolucci, p. 123

17. Long, D.A. (2001). The Raman Effect: A Unified Treatment of the Theory of Raman Scattering by
Molecules. Wiley. ISBN 0-471-49028-8. Chapter 7, Vibrational Resonance Raman Scattering

18. Harris & Berolucci, p. 198

19. Softley, T.P. (1994). Atomic Spectra. Oxford, UK: Oxford University Press. ISBN 0-19-855688-8.

20. Condon, E.V.; Shortley, G.H. (1953). The Theory of Atomic Spectra (https://archive.org/details/in.ernet.
dli.2015.212979) . Cambridge University Press. ISBN 0-521-09209-4.

References

Harris, D.C.; Bert olucci, M.D. (1978). Symmetry and Spectroscopy. Oxford Universit y Press.
ISBN 0-19-855152-5.
Cot t on, F.A. (1990). Chemical Applications of Group Theory (ht t ps://archive.org/det ails/isbn_ 978
0471510949) (3rd ed.). Wiley. ISBN 978-0-471-51094-9.

Further reading

St ant on, L. (1973). "Select ion rules for pure rot at ion and vibrat ion-rot at ion hyper-Raman
spect ra". Journal of Raman Spectroscopy. 1 (1): 53–70. Bibcode:1973JRSp....1...53S (ht t ps://ui.
adsabs.harvard.edu/abs/1973JRSp....1...53S) . doi:10.1002/jrs.1250010105 (ht t ps://doi.org/10.
1002%2Fjrs.1250010105) .

Bower, D.I; Maddams, W.F. (1989). The vibrational spectroscopy of polymers. Cambridge
Universit y Press. ISBN 0-521-24633-4. Sect ion 4.1.5: Select ion rules for Raman act ivit y.

Sherwood, P.M.A. (1972). Vibrational Spectroscopy of Solids. Cambridge Universit y Press.

ISBN 0-521-08482-2. Chapt er 4: The int eract ion of radiat ion wit h a cryst al.

External links

Nat ional Inst it ut e of St andards and Technology (ht t ps://web.archive.org/web/201105140257

17/ht t p://physics.nist .gov/Pubs/At Spec/node17.ht ml)

Lect ure not es from The Universit y of Sheffield (ht t ps://web.archive.org/web/2005042621570

7/ht t p://www.shef.ac.uk/physics/t eaching/phy332/at omic_ physics3.pdf)
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