Chiroptical Spectroscopy

Theory and Applications in Organic Chemistry

Lecture 3: (Crash course in) Theory of optical activity

Masters Level Class (181 041)

Block course, october 2020
62
Crossed polarizers

Chiroptical spectroscopy | Prof. Dr. C. Merten 63

Crossed polarizers and optically active sample

Chiroptical spectroscopy | Prof. Dr. C. Merten 64

Optical rotation: Difference of refractive indices

Linear polarized light can be expressed as superposition

of left and right circular polarized light:
𝑬 𝑬 𝑬

with
𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑
𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑

respectively
𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑
x, y: unit vectors perpendicular to propagation direction

Chiroptical spectroscopy | Prof. Dr. C. Merten 65

Optical rotation: Difference of refractive indices

𝑬 𝑬 𝑬 with

𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑

Taking into account that LCP and RCP light can

have different velocities in a medium: 𝑐
𝑛
𝑣

𝜑 𝜔𝑡 𝜆
𝝀 ⋅

Because  2f, we can rewrite the equation:

𝜑 𝜔𝑡 𝑛𝜔𝑧/𝑐
𝜔𝑡 Δ𝑛 1
𝜑 𝜑∓ 𝑛 𝑛 𝑛
2𝑐 2
Δ𝑛 𝑛 𝑛

Chiroptical spectroscopy | Prof. Dr. C. Merten 66

Optical rotation: Difference of refractive indices

If medium is not circularly birefringant (optically active),

then n=0 and
𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑

Hence, the superposition is

𝑬 𝑬 𝑬 2𝐸 ⋅ 𝒙 ⋅ cos 𝜑

… i.e. it still oscillates in the plane of the direction of

propagation and the unit vector x.

Chiroptical spectroscopy | Prof. Dr. C. Merten 67

Optical rotation: Difference of refractive indices

If the medium shows circular birefringence, we have

𝑬 𝐸 ⋅ 𝒙 ⋅ cos 𝜑 𝐸 ⋅ 𝒚 ⋅ sin 𝜑

and the superposition becomes

𝑬 𝑬 𝑬 𝐸 ⋅ cos 𝜑 cos 𝜑 𝒙 sin 𝜑 sin 𝜑 𝒚

After some rearrangements, we get

z 𝜔 Δ𝑛 z 𝜔 Δ𝑛
𝑬 2𝐸 𝒙 cos 𝒚 sin cos 𝜑
2𝑐 2𝑐

Chiroptical spectroscopy | Prof. Dr. C. Merten 68

Optical rotation: Difference of refractive indices

The exiting ray is still linearly polarized, but its plane is now
rotated by the angle :

z 𝜔 Δ𝑛
𝜃
2𝑐

Consequently, we have a dextrorotatory sample if n+ > n-

and a levorotatory sample if n- > n+

Details on the following equations can be found in

Atkins, Friedman, Molecular Quantum Mechanics, 5th Edition, p. 417

Chiroptical spectroscopy | Prof. Dr. C. Merten 69

How does the refractive index depend on a molecular properties?

From Maxwell equations, we find a relationship with the

relative permittivity r, aka the dielectric constant:
Relative permittivity r directly relates to
electric susceptibility e, which
𝜀 measures how easily a dielectric is
𝑛 𝜀
𝜀 polarized in response to an electic field:
𝜒 𝜀 1

Ok, then:
How does the dielectric constant depend on molecular properties?

For non-polar molecules in a static electric field,

it can be shown that
polarizability 
1 2𝛼𝒩 ⁄ 3𝜀 2 𝜇̂ ⋅ 𝜇̂
𝜀 𝛼
1 𝛼𝒩 ⁄ 3𝜀 3 𝐸 𝐸
with 𝒩 𝑁/𝑉

Chiroptical spectroscopy | Prof. Dr. C. Merten 70

How does the refractive index depend on a molecular properties?

From Maxwell equations, we find a relationship with the

relative permittivity r, aka the dielectric constant:

𝜀 1 2𝛼𝒩 ⁄ 3𝜀 𝒩𝛼
𝑛 𝜀 1
𝜀 1 𝛼𝒩 ⁄ 3𝜀 2𝜀

But the polarizability is not chiral!?

We made a mistake when deriving r from the polarizability !

We assumed 𝑷 𝛼𝒩𝑬
polarizability electric field

This is fully correct if there is a constant electric field.

Chiroptical spectroscopy | Prof. Dr. C. Merten 71

Contribution of the magnetic field

Mistake: We ignored the contribution of the magnetic field to the polarization!

Rewriting our definition of polarization as

𝑷 𝛼𝒩𝑬 𝛽𝒩𝑩

with  being another molecular characteristic and not to be mixed up with the hyperpolarizability!

Chiroptical spectroscopy | Prof. Dr. C. Merten 72

The problem of static polarization

From this definition of the polarization P, we get after solving a few equations again

𝒩𝛼 𝒩𝜔𝛽
𝑛 1
2𝜀 2𝑐𝜀

and thus the difference of the refractive indices becomes

𝒩𝜔𝛽
Δn
𝑐𝜀

For the optical rotation angle, it follows that after passing through a sample of length l,

and taking into account that 0µv = c2 with µv being the vacuum permeability:

z 𝜔 Δ𝑛 𝒩𝑙𝜔 𝛽 1
Δ𝜃 𝒩𝑙 𝜇 𝜔 𝛽
2𝑐 2𝑐 𝜀 2

Chiroptical spectroscopy | Prof. Dr. C. Merten 73

Polarization and quantum mechanics

Polarization P = dipole moment density

𝑁
𝑃 𝜇 ⋅ 𝜇 ⋅𝒩
𝑉

 Quantum mechanical calculation of the induced average

dipole moment 𝜇 should lead to expression for !

Chiroptical spectroscopy | Prof. Dr. C. Merten 74

Schrödinger equation

The time-independent Schrödinger equation

𝐻𝜓 𝜏⃗ E𝜓 𝜏⃗

while the full wavefunction has the form

⁄ℏ
Ψ 𝑡, 𝜏⃗ 𝜓 𝜏⃗ ⋅ 𝑒

It gives us access to observables by evaluating the observables‘ expectation value

Ω Ψ ∗ ΩΨ d𝜏 Ψ|Ω|Ψ

Chiroptical spectroscopy | Prof. Dr. C. Merten 75

The basic idea of perturbation theory

In perturbation theory, we define a (time-dependent) perturbation in the Hamilton

operator:

𝐻 𝑡 𝐻 𝐻 𝑡
e.g. perturbation by electric field

𝐻 𝑡 2µ 𝐸 cos 𝜔𝑡

In presence of a perturbation, the wavefunction is a linear

a t  combination of states:
H1 t

 Ψ 𝑡 𝜓 ⋅𝑒 ℏ 𝑎 𝑡 ⋅𝜓 ⋅ 𝑒 ℏ

For an(t) it can be shown that

1
𝑎 𝑡 𝐻 𝑡 ⋅𝑒 d𝑡
𝑖ℏ
with ℏ𝝎𝒏𝟎 𝑬𝒏 𝑬𝟎
Chiroptical spectroscopy | Prof. Dr. C. Merten 76
Evaluating 𝝁

The expectation value for the average dipole moment (its z-component) is

𝜇 Ψ|𝜇 |Ψ

Taking into account that  is a perturbed wavefunction with

ground state |0⟩ and perturbed states |𝑛⟩, we get

𝜇 0|𝜇 |0 0 𝜇 𝑛 ⋅𝑎 𝑡 ⋅𝑒 𝑛 𝜇 0 ⋅ 𝑎∗ 𝑡 ⋅ 𝑒

𝜇 𝜇 , ⋅𝑎 𝑡 ⋅𝑒 𝜇 , ⋅ 𝑎∗ 𝑡 ⋅ 𝑒

Chiroptical spectroscopy | Prof. Dr. C. Merten 77

Perturbation theory: Magnetically induced polarization

In our case, the perturbation to the Hamiltonian is

𝐻 𝑡 𝜇̂ ⋅ 𝑬 𝑚⋅𝑩
with
𝝁: electric dipole moment operator
𝒎 𝛾𝒍 𝛾 𝒓 𝑝̂ : magnetic dipole moment operator
𝑬: electric field
𝑩: magnetic field

More precisely, we also need to take into account the circular polarization states of the
electric and magnetic field:

𝐻 𝑡 𝜇̂ ⋅ 𝑬 𝑚⋅𝑩
with
𝑬 𝑡 𝐸 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡 and 𝑩 𝑡 𝐵 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡

Chiroptical spectroscopy | Prof. Dr. C. Merten 78

Perturbation theory: Magnetically induced polarization

𝑬 𝑡 𝐸 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡
𝑩 𝑡 𝐵 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡

𝐻 𝑡 𝜇̂ ⋅ 𝑬 𝑚⋅𝑩
𝜇̂ ⋅ 𝐸 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡 𝑚⋅𝐵 𝒙 ⋅ cos 𝜔𝑡 𝒚 ⋅ sin 𝜔𝑡

As 𝜇 𝝁⋅𝒙 and 𝑚 𝒎⋅𝒙

𝐸 𝜇 ⋅ cos 𝜔𝑡 𝜇 sin 𝜔𝑡 𝐵 𝑚 cos 𝜔𝑡 𝑚 sin 𝜔𝑡

1 𝑖
cos 𝛼 𝑒 𝑒 sin 𝛼 𝑒 𝑒
2 2

𝐸 𝜇 ⋅ 𝑒 𝑒 ∓ i𝜇 𝑒 𝑒

𝐵 ∓𝑚 ⋅ 𝑒 𝑒 𝑚 𝑒 𝑒
Chiroptical spectroscopy | Prof. Dr. C. Merten 79
Perturbation theory: Magnetically induced polarization

Based on this perturbation Hamiltonian, the coefficients of the perturbed wavefunctions can
be determined:
1
𝑎 𝑡 𝐻 , 𝑡 ⋅𝑒 d𝑡
𝑖ℏ
with

𝐻 , 𝑡 𝐸 𝜇 ⋅ 𝑒 𝑒 ∓ i𝜇 𝑒 𝑒

𝐵 ∓𝑚 ⋅ 𝑒 𝑒 𝑚 𝑒 𝑒

Then, the induced electric dipole moment is the expectation value of the operator using the
perturbed wavefunctions:

∗
𝜇 Ψ ∗ |𝜇 |Ψ 𝜇 𝜇 ⋅𝑎 𝑡 ⋅𝑒 𝜇 ⋅𝑎 𝑡 ⋅𝑒

Chiroptical spectroscopy | Prof. Dr. C. Merten 80

Perturbation theory: Magnetically induced polarization

Solving the equation for the expectation value

∗
𝜇 Ψ ∗ |𝜇 |Ψ 𝜇 𝜇 ⋅𝑎 𝑡 ⋅𝑒 𝜇 ⋅𝑎 𝑡 ⋅𝑒

leads to the final expression

2 𝜔 2 𝜔
𝜇 Re ⋅𝜇 ⋅𝜇 ⋅𝑬 𝑡 Im ⋅𝜇 ⋅𝑚 ⋅𝑩 𝑡
ℏ 𝜔 𝜔 ℏ 𝜔 𝜔

Comparison with the definition of polarization in an electromagnetic field

𝑷 𝛼𝒩𝑬 𝛽𝒩𝑩
shows that

2 𝜇 ⋅𝑚
𝛽 𝐼𝑚
ℏ 𝜔 𝜔

Chiroptical spectroscopy | Prof. Dr. C. Merten 81

The rotational strength

Taking the rotational average (xx, yy, zz)

2 𝝁 ⋅𝒎
𝛽 𝐼𝑚
3ℏ 𝜔 𝜔

we get

The Rosenfeld equation

𝒩l𝜇 𝜔 𝑅
Δ𝜃
3ℏ 𝜔 𝜔

rotational strength of transition n0

𝑅 𝐼𝑚 𝝁𝟎𝒏 ⋅ 𝒎𝒏𝟎

µ: electric dipole transition moment (EDTM)

m: magnetic dipole transition moment (MDTM)
Chiroptical spectroscopy | Prof. Dr. C. Merten 82
Symmetry properties of the rotational strength

With respect to reflection: EDTM transforms as translation

MDTM transforms as rotation

Requirement for property being achiral:

Sign of R must be conserved upon action of any symmetry element of the molecule

If a molecule has a mirror plane, reflection changes sign of EDTM but not of MDTM.

Consequence: Rotational strength changes sign  R = 0

Chiroptical spectroscopy | Prof. Dr. C. Merten 83

Optical rotatory dispersion (ORD)

The Rosenfeld equation 𝜔 2𝜋𝑓

𝒩l𝜇 𝜔 𝑅
Δ𝜃
3ℏ 𝜔 𝜔
𝜔 𝐸 𝐸 /ℏ

At very high frequencies (𝜔 ≫ 𝜔 ) and in the opposite case of 𝜔 ≪ 𝜔 , the rotational

angle is
Δ𝜃 0
due to the sum rule ∑ 𝑅 0

 OR is close to zero far away from absorption bands, but becomes very large
when approaching them: 𝜔 𝜔 →0

Chiroptical spectroscopy | Prof. Dr. C. Merten 84

Optical rotatory dispersion (ORD)

When 𝜔 𝜔 → 0, i.e. if the excitation frequency is

close to an absorption band, the contribution of that
particular transition dominates the OR value:

𝒩
Δ𝜃
ℏ

 Observation of Cotton effect

„Normal“ ORD curve:

 First resonances in the UV range

 Appears monosignate in usual
range of measurement

Chiroptical spectroscopy | Prof. Dr. C. Merten 85

Outline of the lecture

Dates topics

 Monday Introduction

 Polarization of light

 Tuesday Theoretical basis of optical activity

Optical rotation
Wednesday Circular dichroism
Circular dichroism

Thursday Vibrational optical activity

Vibrational optical activity

Oct 22? applications

your part
Oct 29? applications

Chiroptical spectroscopy | Prof. Dr. C. Merten 86