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BEFORE AFTER
hν (No more photon)
Molecule in Molecule in
ground state excited state
This quantum mechanical picture may satisfy conservation of energy (when you
quantize light and molecular energies), but it has lots of problems and doesn’t tell
you much.
( ) () (
E r, t = ε̂ r E o cos ωt − k ⋅ r − φ )
Polarization vector Wavevector defines
direction of propagation
Amplitude
Frequency (rad/sec)
To simplify:
(1) Propagate along x̂ ; (2) φ = 0 (for the time being we will drop the polarization)
E ( x, t ) = E o cos ( ωt − kx )
2π
λ= oscillations in space
k
E
E0
x
propagating at c
2π 1
time : = oscillations in time
ω ν
Now, we will drop wave vector ( k → 0 , since λ>>x and we consider molecules at x=0)
c
E ( t ) = E o cos ωt
2
I= Eo
4π
2π ω
k = =
λ c
c = 2.998 × 108 m / s
Why should we be able to call molecules harmonic oscillators? i.e., a mass on a spring?
The covalent bond can be thought of as a spring. The equilibrium length is a balance
1 ⎛⎜ ∂ 2 V ⎞⎟
V(q ) = (q − q0 )2
2 ⎜⎝ ∂q 2 ⎟⎠
1 2
= kQ
2
q0 q
Q=0
(Set Q = q − q0)
∂V
Linear restoring force: Fres = − = −kQ
∂Q
∂ 2Q
Equation of Motion from Newton F = ma m
∂t 2
∂ 2Q
m 2 = Fres + Fdamp + Fext driving force
∂t
∂Q
= −kQ − b + Fext
∂t
∂ 2Q b ∂Q kQ Fext
+ + =
∂t 2 m ∂t m m
with light field
Fext (t ) = Fo cos ωt
Solutions:
∂ 2Q
m 2
+ kQ = 0
∂t
Solution:
Q ( t ) = A sin ( ωo t ) + B cos ( ωo t )
k
resonance frequency: ωo =
m
Q
A
2π
ω0
b) Now we add damping—H.O. may feel friction that reduces the amplitude of
oscillation
∂ 2Q ∂Q
m 2 = Fres + Fdamp = − kQ − b
∂t ∂t
∂ 2Q b ∂Q kQ
+ + =0
∂t 2 m ∂t m
2
γ = b / 2m Ω o = ωo − γ 2 ≈ ωo
2π
Ω0
The effect depends on the frequency of the driving field . . . like pushing someone on
a swing.
• When you drive the system with frequency ω ≈ ω o there will be an efficient
transfer of power and the displacement of the H.O. will increase
Indeed, that is what an absorption spectrum is! Measure the power absorbed by the
system from the field.
Set: F0 ∝ E0
Fext ( t ) = Fo cos ωt
Fo m
Q ( t ) = A sin ( ωt + β ) = sin ( ωt + β )
( ( ω − ω ) + 4γ ω )
1
2 2
2
2 2 2
o
ω2o − ω2
tan β =
2 γω
(ω − ω2 ) = ( ωo − ω) ( ωo + ω) ≈ 4ω2o ( ωo − ω)
2 2 2 2 2
o
Fo 1
Q(t) = sin ( ωt + β )
2mωo ⎡ ω − ω 2 + γ 2 ⎤ 2
1
⎣( o ) ⎦
∂Q
Pavg = F(t) ⋅
∂t avg
(avera
Average over several cycles
γF0
2 1
=
2m ( ω − ω )2 + γ 2
LORENTZIAN LINESHAPE
peak is at ω = ωo
F02
At what frequency
4mγ shift relative to
maximum is the
Pav(ω) absorbed power
reduced by ½?
γ
ω − ω o = ±γ
ω0 ω
peak → ω o width → γ
4m
Well, you can see from the spectrum that we have been able to determine ω o and γ.
A
2γ
ω0 ω
ω0
≅ 3000cm−1 γ ≅ 15cm −1
2π c
2π −14
= τ = 1 × 10 s 10 fs
ω0
k
ω0 =
m
Now for the mass m we want to use the reduced mass μ or mR. (This is the
effective mass: we need this for 2 masses on a spring with a fixed center of mass.)
mAmB
μ = mR = for a diatomic molecule A-B.
m A + m B
m R ( H 35Cl ) = 0.97 ( ω0 ) A ( mR )B
=
m R ( D35Cl ) = 1.89 ( ω0 ) B ( mR )A
Therefore, we predict:
ω0 ( DCl ) → 2150cm −1
What is a?
Dipole moment:
μ H
μ = Σ q l δ+
Cl
charge
distance δ-
In an electric field, this dipole will feel a force.
V = −μ ⋅ E
∂V ⎛ ∂μ ⎞
F=− =⎜ ⎟⋅E
∂Q ⎝ ∂Q ⎠
Polarity isn’t a sufficient criterion: CO2 is nonpolar but still a strong absorber of infrared
radiation. This occurs as a result of radiation inducing distortions of the molecule
along the symmetry axis (asymmetric stretch) or perpendicular to the symmetry
axis (bend).
∂μ
F0 = E 0 cos θ (…for a single molecule)
∂Q
You can study a crystal where all molecules have the same orientation, and how
by rotating the light polarization, you can tell how different vibrations are
oriented.
Summary:
Absorption spectra are characterized by:
• Resonance Frequency k
ωo =
m
2
πF02 π2 ∂μ
• Integrated Peak Amplitude =I cos 2 θ
4m mc ∂Q