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8. Radiative Transition and Selection Rules
8.1 Radiative Transition
(i) Let electron is in state n whose wave function is
iE iE
n t n t
n x, t n e and n* x, t n*e
(ii) The expectation value x of the position of such electron is
x n* x, t x n x, t dx *
x x x dx
n n
ks
x independent of time (non oscillatory therefore electron in fixed state does not
radiate)
(iii) Assume electron falls from state m to state n. The wave function of electron during
transition is
x, t a n x, t b m x, t
(iv) The expectation value x for this electron is
zi
* *
x x, t x x, t dx x a x, t b x, t
n m x a n x, t b m x, t dx
E E
i m n t
x a2 x n* x n x dx ba x m* x n x e dx
E E
i m n t
ab x n* x m x e dx b2 *
x x x dx
m m
(v) The 1st and last term do not vary with time, while 2 nd & 3rd are time variable &
fi
contribute to x . These two terms becomes
E En * *
cos m
t x ab m x n x ab n x m x dx
E En * *
i sin m
t x ab m x n x ab n x m x dx
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fiziks
Institute for NET/JRF, GATE, IIT-JAM, JEST, TIFR and GRE in PHYSICAL SCIENCES
(vi) The real part of this result varies with time as
E En Em En E En
cos m t cos 2 t cos 2 t where m
h h
(vii) The electron position therefore, oscillates sinusoidally at frequency and hence
radiative transition.
8.2 Transition Rule
(i) The general condition for an atom in an excited state to radiate is that the integral
ks
*
x, t x x, t dx
n n not be zero, since the intensity of the radiation is proportional to
it.
(ii) Transition for which this integral is finite is called allowed transition, while those for
which it is zero are called Forbidden transition.
(iii) In case of hydrogen atom, 3 quantum numbers are needed to specify the initial and
final states involved in a radiative transition. There are n, l, & ml.
(iv) It is represent either x, y, or z coordinate, the condition for an allowed transition is
zi
u
n ,l , ml n ',l ',m 'l dV 0
where u is taken as x, the radiation would be that produced by a dipole antenna lying on
the x-axis
(v) It is found that the only transition between states of different n that can occur are
those in which the orbital quantum number l changes by + 1 or -1 and the magnetic
quantum number ml does not change or changes by + 1 or – 1.
fi
The condition for allowed transition is
l 1
Selection rules
ml 0, 1
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fiziks, H.No. 40 D, G.F, Jia Sarai, Anand Institute of Mathematics,
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Institute for NET/JRF, GATE, IIT-JAM, JEST, TIFR and GRE in PHYSICAL SCIENCES
Selection rules for electric dipole transitions
One-electron atoms without spin
This includes all the hydrogenic systems, the alkalis and the singly ionized alkaline earth
elements, etc. The selection rules are as follows.
(a) The parity of the wave function must change.
(b) No restriction on total quantum number ‘n’
(c) ∆l = ± 1;
(d) ∆ms = 0 ;
ks
(e) ∆ml = 0, ± 1
Polarization of the Radiation
The wave emitted in transitions for which ∆ml = +1 is left circularly polarized when
observed from the positive z-axis and is labeled a * . Similarly transitions for which
∆ml = -1 in emission correspond to right circularly polarized radiation when observed
from the direction 0 and are labeled a .
One-electron atoms with spin
(a) The parity of the wave function must change.
zi
(b) No restriction on total quantum number ‘n’
(c) ∆ j = 0, ± 1 (But j = 0 ↔ j = 0)
(d) ∆mj = 0, ± 1
Many-electron atoms
(a) ∆L = 0, ± 1 (but L = 0 0 is forbidden.)
(b) ∆mL = 0, ± 1
fi
(c) ∆J = 0, ± 1 (but J = 0 0 is forbidden.)
(d) ∆mJ = 0, ± 1
(e) ∆S = 0
(f) ∆MS = 0
Head office Branch office
fiziks, H.No. 40 D, G.F, Jia Sarai, Anand Institute of Mathematics,
Near IIT, Hauz Khas, New Delhi-16 28-B/6, Jia Sarai, Near IIT
Phone: 011-26865455/+91-9871145498 Hauz Khas, New Delhi-16
Website: www.physicsbyfiziks.com
Email:
[email protected] 40
