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Chapter 14Radiating Dipoles in Quantum Mechanics
P. J. Grandinetti
Chem. 4300
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Electric dipole moment vector operatorElectric dipole moment vector operator for collection of charges is
๐ =Nโ
k=1qkr
Expectation value for electric dipole moment vector is
โจ๐(t)โฉ = โซVฮจโ(r, t) ๐ฮจ(r, t)d๐
The time dependent energy eigenstates are given by
ฮจn(r, t) = ๐n(r)eโiEntโโ
Letโs focus electric moment of single bound charged QM particle.
๐ = โqer = โqe
[xex + yey + zez
]P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Time dependence of electric dipole momentEnergy EigenstateStarting with
โจ๐(t)โฉ = โซVฮจโ
n(r, t) ๐ฮจn(r, t)d๐ = โซVฮจโ
n(r, t)(โqe
r)ฮจn(r, t)d๐
Inserting energy eigenstate, ฮจn(r, t) = ๐n(r)eโiEntโโ, gives
โจ๐(t)โฉ = โซV๐โ
n (r)eiEntโโ
(โqe
r)๐n(r)eโiEntโโd๐
Time dependent exponential terms cancel out leaving us with
โจ๐(t)โฉ = โซV๐โ
n (r)(โqe
r)๐n(r)d๐ No time dependence!!
No bound charged quantum particle in energy eigenstate can radiate away energy as lightor at least it appears that way โ Good news for Rutherfordโs atomic model.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
But then how does a bound charged quantum particle in anexcited energy eigenstate radiate light and fall to lower energy eigenstate?
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Time dependence of electric dipole moment - A Transition
During transition wave function must change from ฮจm to ฮจn
During transition wave function must be linear combination of ฮจm and ฮจn
ฮจ(r, t) = am(t)ฮจm(r, t) + an(t)ฮจn(r, t)
Before transition we have am(0) = 1 and an(0) = 0
After transition am(โ) = 0 and an(โ) = 1
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Time dependence of electric dipole moment - A TransitionTo maintain normalization during transition we require
|am(t)|2 + |an(t)|2 = 1.
Electric dipole moment expectation value for ฮจ(r, t) is
โจ๐(t)โฉ = โซVฮจโ(r, t) ๐ฮจ(r, t)d๐
= โซV
[aโm(t)ฮจ
โm(r, t) + aโn(t)ฮจ
โn(r, t)
] ๐ [am(t)ฮจm(r, t) + an(t)ฮจn(r, t)]
d๐
โจ๐(t)โฉ = aโm(t)am(t)โซVฮจโ
m(r, t) ๐ฮจm(r, t)d๐ + aโm(t)an(t)โซVฮจโ
m(r, t) ๐ฮจn(r, t)d๐
+ aโn(t)am(t)โซVฮจโ
n(r, t) ๐ฮจm(r, t)d๐ + aโn(t)an(t)โซVฮจโ
n(r, t) ๐ฮจn(r, t)d๐
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Time dependence of electric dipole moment - A Transition
โจ๐(t)โฉ = aโm(t)am(t)โซVฮจโ
m(r, t) ๐ฮจm(r, t)d๐โโโโโโโโโโโโโโโโโโโโโโโโโ
Time Independent
+ aโm(t)an(t)โซVฮจโ
m(r, t) ๐ฮจn(r, t)d๐
+ aโn(t)am(t)โซVฮจโ
n(r, t) ๐ฮจm(r, t)d๐ + aโn(t)an(t)โซVฮจโ
n(r, t) ๐ฮจn(r, t)d๐โโโโโโโโโโโโโโโโโโโโโโโ
Time Independent
1st and 4th terms still have slower time dependence due to an(t) and am(t) but this electric dipolevariation will not lead to appreciable energy radiation.Drop these terms and focus on faster oscillating 2nd and 3rd terms
โจ๐(t)โฉ = aโm(t)an(t)โซVฮจโ
m(r, t) ๐ฮจn(r, t)d๐ + aโn(t)am(t)โซVฮจโ
n(r, t) ๐ฮจm(r, t)d๐
Two integrals are complex conjugates of each other.Since โจ๐(t)โฉ must be real we simplify to
โจ๐(t)โฉ = โ{
aโm(t)an(t)โซVฮจโ
m(r, t) ๐ฮจn(r, t)d๐}
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Time dependence of electric dipole moment - A Transition
โจ๐(t)โฉ = โ{
aโm(t)an(t)โซVฮจโ
m(r, t) ๐ฮจn(r, t)d๐}
Inserting stationary state wave function, ฮจn(r, t) = ๐n(r)eโEntโโ, gives
โจ๐(t)โฉ = โ{
aโm(t)an(t)[โซV๐โ
m(r) ๐๐n(r)d๐โโโโโโโโโโโโโโโโโโโโโโโโจ๐โฉmn
]ei(EmโEn)tโโ
}
๐mn = (Em โ En)โโ is angular frequency of emitted light andโจ๐โฉmn is transition dipole momentโpeak magnitude of dipole oscillation
โจ๐โฉmn = โซV๐โ
m(r) ๐๐n(r)d๐
Finally, write oscillating electric dipole moment vector asโจ๐(t)โฉ = โ{
aโm(t)an(t) โจ๐โฉmn ei๐mnt}P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Transition dipole momentIn summary, the superposition state
ฮจ(r, t) = am(t)ฮจm(r, t) + an(t)ฮจn(r, t)
has oscillating electric dipole moment vector
โจ๐(t)โฉ = โ{
aโm(t)an(t) โจ๐โฉmn ei๐mnt}where
โจ๐โฉmn = โซV๐โ
m(r) ๐๐n(r)d๐
๐mn = (Em โ En)โโ is angular frequency of emittedlight
aโm(t)an(t) gives time scale of transition.โจ๐โฉmn is transition dipole momentโamplitude ofdipole oscillation
Integrals give transition selection rules for various spectroscopies(๐x)
mn = โซV๐โ
m๏ฟฝ๏ฟฝx(t)๐nd๐,(๐y)
mn = โซV๐โ
m๏ฟฝ๏ฟฝy(t)๐nd๐,(๐z)
mn = โซV๐โ
m๏ฟฝ๏ฟฝz(t)๐nd๐
where ๐2mn = |||(๐x
)mn|||2 + |||(๐y
)mn|||2 + |||(๐z
)mn|||2
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Okay, so...
Wave function in superposition of energy eigenstates can have oscillating electric dipolemoment which will emit light until system is entirely in lower energy state.
But how does atom in higher energy eigenstate get into this superposition of initial andfinal eigenstates in first place?
One way to shine light onto the atom. The interaction of the atom and light leads toabsorption and stimulated emission of light.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Rate of Light AbsorptionPotential energy of ๐ of quantum system interacting with a time dependent electric field, (r, t) is
V(t) = โ ๐ โ (r, t) = โ ๐ โ 0(r) cos๐t
and Hamiltonian becomes (t) = 0 + V(t).
When time dependent perturbation is present old stationary states of 0 (before light was turnedon) are no longer stationary states.
Even if molecule or atom has no permanent electric dipole moment, the electric field can induce anelectric dipole moment. If electric field is oscillating we expect induced electric dipole to oscillate.
V(t) = โ ๐(t) โ 0(r) cos๐t
If light wavelength is long compared to system size (atom or molecule) we can ignore rdependence of and assume system is in spatially uniform (t) oscillating in time. Holds foratoms and molecules until x-ray wavelengths and shorter.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Rate of Light AbsorptionTo describe time dependence of electric dipole moment write wave function as linearcombination of stationary state eigenfunction of 0, i.e., when V(t) is absent.
ฮจ(r, t) =nโ
m=1am(t)ฮจm(r, t)
Need to determine time dependence of am(t) coefficients.As initial condition take |an(0)|2 = 1 and |amโ n(0)|2 = 0.Putting (t) = 0 + V(t) and ฮจ(r, t) into time dependent Schrรถdinger Equation
(t)ฮจ(r, t) = iโ๐ฮจ(r, t)๐t
and skipping many steps we eventually get
dam(t)dt
โ โ iโ โซV
ฮจโm(r, t)V(t)ฮจn(r, t)d๐
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Rate of Light AbsorptionUsing our expression for V(t) and ฮจn = ๐neโiEntโโ we get
dam(t)dt
โ โ iโ โซV
ฮจโm(r, t)V(t)ฮจn(r, t)d๐ = โ i
โ
[โซV๐โ
m๐(t)๐nd๐
]โโโโโโโโโโโโโโโโโโโโโ
transition moment integral
ei๐mnt โ 0 cos๐t
Setting |an(0)|2 = 1 and |am(0)|2 = 0 for n โ m (after many steps) we find
||am(t)||2 =โจ๐mnโฉ2t6๐0โ2 u(๐mn)
u(๐mn) is radiation density at ๐mn = ๐mnโ2๐.Rate at which n โ m transition from absorption of light energy occurs is
Rnโm =||am(t)||2
t=
โจ๐mnโฉ2
6๐0โ2 u(๐mn)
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Okay, but what about spontaneous emission?An atom or molecule in an excited energy eigenstate can spontaneously emit light and return to itsground state in the absence of any electromagnetic radiation, i.e., V(t) = 0
How does spontaneous emission happen?
In this lectureโs derivations we treat light as classical E&M wave. No mention of photons.
Treating light classically gives no explanation for how superposition gets formed.
To explain spontaneous emission we need quantum field theory, which for light is called quantumelectrodynamics (QED).
Beyond scope of course to give QED treatment.
Instead, we examine Einsteinโs approach to absorption and stimulated emission of light and seewhat he learned about spontaneous emission.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and Emission (Meanwhile, back in 1916)
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and Emission (Meanwhile, back in 1916)Before any of this quantum theory was worked out. At this time Einstein used Planckโs distribution
u(๐) = 8๐๐2
c30
(h๐
eh๐โkBT โ 1
)to examine how atom interacts with light inside cavity full of radiation.
For Light Absorption he said atomโs light absorption rate, Rnโm, depends on light frequency,๐mn, that excites Nn atoms from level n to m, and is proportional to light intensity shining on atom
Rnโm = NnBnmu(๐mn)
Bnm is Einsteinโs proportionality constant for light absorption.For Light Emission, when atom drops from m to n level, he proposed 2 processes: SpontaneousEmission and Stimulated Emission
Absorption StimulatedEmission
SpontaneousEmission
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and Emission (Meanwhile, back in 1916)Spontaneous Emission: When no light is in cavity, atom spontaneously radiates awayenergy at rate proportional only to number of atoms in mth level,
Rspontmโn = NmAmn
โถ Amn is Einsteins proportional constant for spontaneous emission.โถ Einstein knew oscillating dipoles radiate and he assumed same for atom.โถ Remember, in 1916 he wouldnโt know about stationary states and Schrรถdinger Eq.
incorrectly predicting atoms do not spontaneously radiate.
Stimulated Emission: From E&M Einstein guessed that emission was also generated byexternal oscillating electric fieldsโlight in cavityโand that stimulated emission rate isproportional to light intensity and number of atoms in mth level.
Rstimulmโn = NmBmnu(๐mn)
Bmn is Einsteinโs proportional constant for stimulated emission.P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and Emission (Meanwhile, back in 1916)Taking 3 processes together and assuming that absorption and emission rates are equal atequilibrium
Rnโm = Rspontmโn + Rstimul
mโn
we obtainNnBnmu(๐mn) = Nm[Amn + Bmnu(๐mn)]
Einstein knew from Boltzmannโs statistical mechanics that n and m populations at equilibriumdepends on temperature
NmNn
= eโ(EmโEn)โkBT = eโโ๐โkBT
We can rearrange the rate expression and substitute for NmโNn to get
Amn + Bmnu(๐mn) =NnNm
Bmnu(๐mn) = eโ๐โkBTBnmu(๐mn)
and then getu(๐mn) =
Amn
Bnmeโ๐โkBT โ BmnP. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and Emission (Meanwhile, back in 1916)Einstein compared his expression to Planckโs
u(๐mn) =Amn
Bnmeโ๐โkBT โ Bmnโโโโโโโโโโโโโโโโโโโโโโโ
Einstein
=8๐๐2
mn
c30
(h๐mn
eh๐โkBT โ 1
)โโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
Planck
Bnm = Bmn, i.e., stimulated emission and absorption rates must be equal to agree with Planck.
u(๐mn) =AmnBnm
(1
eโ๐โkBT โ 1
)โโโโโโโโโโโโโโโโโโโโโโโโโโโ
Einstein
=8๐๐2
mn
c30
(h๐mn
eh๐โkBT โ 1
)โโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
Planck
Relationship between spontaneous and stimulated emission rates:
AmnBnm
=8๐๐2
mn
c30
h๐mn =8๐h๐3
mn
c30
Amazing Einstein got this far without full quantum theory.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Light Absorption and EmissionFast forward to Schrรถdingerโs discovery of quantum wave equation, which gives light absorption rate as
Rnโm =โจ๐mnโฉ2
6๐0โ2 u(๐mn) = Bmnu(๐mn)
setting this equal to Einsteinโs rate for absorption gives
Bmn =โจ๐mnโฉ2
6๐0โ2
from which we can calculate the spontaneous emission rate
Amn =8๐h๐3
mn
c30
โจ๐mnโฉ2
6๐0โ2
For H atom, spontaneous emission rate from 1st excited state to ground state is โผ 108/s inagreement with what Amn expression above would give.QED tells us that quantized electromagnetic field has zero point energy.It is these โvacuum fluctuationsโ that โstimulateโ charge oscillations that lead to spontaneousemission process.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Selection Rules for Transitions
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Transition Selection Rules
In all spectroscopies you find that transition rate between certain levels will be nearly zero.
This is because corresponding transition moment integral is zero.
For electric dipole transitions we found that transition rate depends on
โจ๐โฉmn = โซV๐โ
m(r) ๐๐n(r)d๐
๐m and ๐n are stationary states in absence of electric field.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Harmonic Oscillator Selection RulesConsider quantum harmonic oscillator transitions.
Imagine oscillating dipole moment of charged particle in harmonic oscillator potential orvibration of diatomic molecule with electric dipole moment.
This is 1D problem so we write electric dipole moment operator of harmonic oscillator inseries expansion about its value at equilibrium
๐(r) = ๐(re) +d๐(re)
dr(r โ re) +
12
d2๐(re)dr2 (r โ re)2 +โฏ
1st term in expansion, ๐(re), is permanent electric dipole moment of harmonic oscillatorassociated with oscillator at rest.
2nd term describes linear variation in electric dipole moment with changing r.
We will ignore 3rd and higher-order terms in expansion.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Harmonic OscillatorPlug 1st two terms of expansion into transition moment integral
โจ๐nmโฉ = โซโ
โโ๐โ
m(r)(๐(re) +
d๐(re)dr
(r โ re))๐n(r)dr,
=๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ:0๐(re)โซ
โ
โโ๐โ
m(r)๐n(r)dr +(
d๐(re)dr
)โซ
โ
โโ๐โ
m(r)(r โ re)๐n(r)dr
Since m โ n we know that 1st integral is zero as stationary state wave functions are orthogonal leavingus with โจ๐nmโฉ = (
d๐(re)dr
)โซ
โ
โโ๐โ
m(r)(r โ re)๐n(r)dr
In quantum harmonic oscillator it is convenient to transform into coordinate ๐ using x = r โ re and๐ = ๐ผx to obtain โจ๐nmโฉ = (
d๐(re)dr
)โซ
โ
โโ๐โ
m(๐)๐๐n(๐)d๐
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Harmonic OscillatorWith harmonic oscillator wave function, ๐n(๐), we obtain
โจ๐nmโฉ = (d๐(re)
dr
)AmAn โซ
โ
โโHm๐Hneโ๐
2d๐
Using recursive relation, ๐Hn = 12 Hn+1 + nHnโ1, we obtain
โจ๐nmโฉ = (d๐(re)
dr
)AmAn
[12 โซ
โ
โโHmHn+1eโ๐
2d๐ + nโซ
โ
โโHmHnโ1eโ๐
2d๐
]To simplify expression we rearrange
AmAn โซโ
โโHm(๐)Hn(๐)eโ๐
2d๐ = ๐ฟm,n to โซ
โ
โโHm(๐)Hn(๐)eโ๐
2d๐ =
๐ฟm,n
AmAn
Substitute into expression for โจ๐nmโฉ gives
โจ๐nmโฉ = (d๐(re)
dr
)[12
AnAn+1
๐ฟm,n+1 + nAn
Anโ1๐ฟm,nโ1
]P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Harmonic OscillatorRecalling
An โก 1โ2nn!๐1โ2
we finally obtain transition dipole moment for harmonic oscillator
โจ๐nmโฉ = (d๐(re)
dr
)[โn + 1
2๐ฟm,n+1 +
โn2๐ฟm,nโ1
]
For absorption, m = n + 1, transition is n โ n + 1 and โจ๐mnโฉ2 gives
Rnโn+1 =u(๐mn)6๐0โ2 โจ๐mnโฉ2 =
u(๐mn)6๐0โ2
(d๐(re)
dr
)2 n + 12
For emission, m = n โ 1, transition is n โ n โ 1 and โจ๐mnโฉ2 gives
Rnโnโ1 =u(๐mn)6๐0โ2 โจ๐mnโฉ2 =
u(๐mn)6๐0โ2
(d๐(re)
dr
)2 n2
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics
Harmonic Oscillator
Rnโn+1 =u(๐mn)6๐0โ2
(d๐(re)
dr
)2 n + 12
and Rnโnโ1 =u(๐mn)6๐0โ2
(d๐(re)
dr
)2 n2
Selection rule for harmonic oscillator is ฮn = ยฑ1.
Also, for allowed transitions(d๐(re)โdr
)must be non-zero.
For allowed transition it is not important whether a molecule has permanent dipolemoment but rather that dipole moment of molecule varies as molecule vibrates.
In later lectures we will examine transition selection rules for other types of quantizedmotion, such as quantized rigid rotor and orbital motion of electrons in atoms andmolecules.
P. J. Grandinetti Chapter 14: Radiating Dipoles in Quantum Mechanics