Principles of Molecular Spectroscopy

What variables do we need to characterize a molecule? Nuclear and electronic configurations: What is the structure of the molecule? What are the bond lengths? How strong or stiff are the bonds? What is the symmetry? Where is the electron density? Molecular Behavior: How much do the nuclei move (vibration/rotation)? How do the structural variables change with time?

EXAMPLE: H-F What is your picture of the structure of this molecule? 2 nuclei + 10 e? Molecular orbitals?
ab
1s 2pz

H b = c1 1s + c 2 F z 2p H F ab = c 2 1s c1 2pz

We quantitatively characterize the structure through the electronic energy as a function of nuclear configuration:

Eelec
ab

0
b

-Do
repulsive forces

attractive forces

re
Eelec = electronic energy relative to isolated atoms

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If we characterize this energy curve, we have learned much about our molecule: 1) re: What is the equilibrium separation between atoms?
2) D0: What is the strength of the bond? How stable is molecule?
3) Shape of b or ab: Is re fixed? How stiff is bond? How does re change if you put energy
into bond? 4) Splitting between surfaces: What is the nature and energy of the e orbitals involved in bonding? How can you probe these energy surfaces with light? Light resonant with the motion of charged particles such as electrons or nuclei will be absorbed. We need rules for the frequency or energy of motion of nuclei and electrons. These will be related to the parameters above. What we will find is that different spectroscopies will tell us about different variables: Rotational spectroscopy: will tell us where re is.
Vibrational spectroscopy: will tell us how stiff the bond is and about the curvature of potential.
Electronic spectroscopy: will tell us about where electronic states lie
potential energy curves, barriers, dissociation energies Change to a new frame of reference - molecular coordinates For any free particle (nucleus or electron): Kinetic and potential energy associated with the motion of a particle Translation along x, y, z n particles 3n degrees of freedom (d.o.f).
x z

In a molecule the positions of these particles is not independent. To solve problems in molecular structure and motion, chose a molecular frame of reference: Coordinates along symmetry axes
Origin (often) at the center of mass

ro = 1

miri

i
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5.33 Lecture Notes: Principles of Molecular Spectroscopy

To simplify problem, treat nuclear and electronic motion separately.

Electrons are much lighter than nuclei. Therefore, we expect that the electrons will occupy a fixed distribution in space about a nuclear configuration. Separate different types of motion based on time-scale or energy of motion. 5.61: The basis for drawing potential energy curves is the Born-Oppenheimer Approximation: Motion of electron is much faster than nuclei; doesnt depend on nuclear kinetic energy.

Electrons: The spatial extent motion is described by atomic or molecular orbitals. We will return to this later.

Nuclei: Three types of motion for nuclei with respect to the c.o.m. of the molecule:

Consider a diatomic (with 6 d.o.f).

Displacement of atoms relative to one another / C.O.M. fixed

2) Rotation

Motion about C.O.M. / C.O.M. fixed

3) Translation

move C.O.M.

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>

For a polyatomic (n atoms) 3n degrees of freedom Linear 3n5 2 3 Nonlinear 3n6 3 3

Vibrational: Rotational: Translational:

Normal Modes

How are these motions related to the structure of the molecule? How do these reflect electronic potential?

A classical description allows you to say a lot about spectroscopy, but it doesnt explain experiments very well! We need quantum mechanics! Classically: No restriction on energy of system or spatial configuration (We can add or remove energy continuously.) Position and motion of particles with arbitrary accuracy Quantum: Energy levels are quantized Quantum mechanics tells us that these energies are not continuous but discrete.

Fixed energy and spatial configuration (eigenvalues & eigenstates) We have discrete states (i) with spatial structure, and fixed energy. These eigenstates define the extent of motion of a particle with a unit of energy, and no fractional amount is allowed. Probabilistic description of particle position and motion. Superpositions: ( r ) = ci i ( r )
i

We represent the state of the system through quantum numbersusually integers. The energy is related to these numbers. Ground State : configuration of electrons, nuclei, (a set of quantum numbers) that represent the lowest energy state of the system.

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Electronic States:

We already started this lecture talking about atomic + molecular orbitals, which represent discrete energy states that electrons can occupy. You describe these through discrete quantum numbers, i.e. for atom: n, l, m, ms
n: principle quantum number; l: orb. ang. mom.; m: degeneracy; ms: spin

These states have definite energy and electron density distribution (spatial dimension). There is no way for an electron to occupy an intermediate energy between quantized values. The energy to move an electron from the ground (lowest energy) state to another is a lot: Typically 20,000-100,000 cm-1 = 10-50 kJ/mol. This corresponds to UV and visible light, ~100-500nm For polyatomic molecules, we can use linear combinations of atomic orbitals.

Quantization of nuclear degrees of freedom:

The vibration, rotation, and translation of the 3n nuclear d.o.f. of a molecule are also quantized.
Vibrations: Classically I can put any energy I want into vibrational motion moves energy levels to higher displacement. For a harmonic oscillator:

E=V+T=

1 2 p2 kQ + 2 2m
Q

Q(t) = A sin 0t

Quantum mechanics says there are discrete vibrational energy levels corresponding to specific vibrational states (wave functions).

E E0

E2 E1

Each vibrational state has a probability distribution that tells me the probability of finding nuclei in particular position. (Similar to electronic states)
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For a quantum mechanical harmonic oscillator, (the simplest quantum mechanical model for a vibration)

The energies of these discrete vibrational energy levels is:

E v = E vib = 0 ( v + 1 ) 2

0 =

k = 2 0 mR

0 3000 300 cm 1

v is the vibrational quantum number, v = 0,1,2 Even in lowest state E 0 = h0 / 2 . Spacing between vibrational levels uniform
E = E v E v 1 = h 0

The proportionality constant between vibrational frequency and energy is Plancks constant h = 6.626 1034 J s So if we can measure Ev determine 0 determine k.

Rotation: Classically, rotation of a free object is governed by angular momentum L=I

is the angular velocity ( =2v)

2 Moment of Inertia: I = m R R e

or I = mi ri2
i

The energy of free rotational motion is all kinetic: p

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Classically, the more energy I put into a rigid rotor, the faster it rotates higher angular momentum.
Quantum mechanically rotational angular momentum is quantized.

E rot =
L =

L 2
2I

still holds, but L is quantized

J = 0,1,2,3 (rotational angular momentum quantum number)

J (J + 1)
2

E rot =

2I

J ( J + 1) =

h J ( J + 1) hcBJ ( J + 1) 82 I

B=

h
8 2cI

Rotational levels are not equally spaced. Rotational levels have degeneracy. MJ = 0 J ; g(J) = (2J+1) Rotational spectroscopy: measure Erot determine B I R e !

TRANSLATION: (motion of center of mass)

Quantum mechanically: Energy levels given by particle-in-a-box One-dimension: E trans = n2h2 8ma 2 n = 1, 2
a: length of box

This only matters for very small boxes. Free space: a ; energy levels are continuous.

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Quantum mechanical energies are summed over all degrees of freedom:

E total = E electronic + E vibrational + E rotational + E translational + E nuclear + ...

E = E elec + 0 (v + 1 ) + hcB J (J + 1) + 2
E 50,000 cm-1

~1,000 cm-1

~1-10cm 1

v = 0,1,2 J = 0,1,2

specify energy through a set of quantum numbers, and characteristic vib./rot./etc. constants

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LIGHT:

Classically we talked about a light field driving a classical H.O. The external field allows us to drive the H.O. to higher displacement, the efficiency of displacing the oscillator depended on resonance: = 0 How is this compatible with quantum energy levels? To drive a quantum H.O. to higher amplitude higher energies higher V transitions are discrete!

Light drives transitions between discrete states. Transition requires resonance. Light is also quantized: E = h = Resonance Energy conservation Energy of light = Energy difference between initial (i) and final (f) states

E = E f Ei

E f Ei

fi

Absorption features related to energy level splittings!

These transitions can be between different electronic, vibrational, rotational states: E field = E elec + E vib + E rot +
Spectroscopy Light Freq. Transitions

Electronic Rot-vib.: pure rot.:

UV/Vis IR/Raman FIR/wave

104-105 cm-1 102-103 cm-1 10-1-101 cm-1

electronic (+ vib + rot) vibrational (+ rot) rotational

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In a quantum system . . . what does light do to quantum states?

Quantum eigenstates are time-independent (stationary). There is no motion.

We shouldnt think of absorption as taking molecules from one eigenstate and putting it in anotherthats not quite correct. Rather, the light couples these two states together.

What happens after turning on the light field?

(t) = c0 (t) 0 + c1 (t)

P1 = c1
(t)
2

sin 2
( E1 E 0 ) t /

P0 = 1
c
(t) 1

cos 2
( E1 E 0 ) t /

The probability of finding the system in one state oscillates back and forth.

PTOT = c0 (q, t) + c1 (q, t)

Ptot

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Intensity of Absorption Lines

N = N f Ni
The population of a quantum state the fraction of molecules occupying that state is dictated by the temperature. For many molecules, the particles distribute themselves through quantum states. Lowest E state is most probable. At T = 0 K all molecules are in the ground statelowest electronic state, v = 0, J = 0 .
The equilibrium thermal energy of a collection of molecules has is characterized by the temperature.
E T

The fraction of molecules occupying a quantum level of energy Ei at a temperature T is described by the

Boltzmann distribution (a probability function):

Nj is the fraction of molecules in state j. gj is the degeneracy of the jth state. q, the partition function, is a sum over the population of all states q = j g j exp( E j / k BT) . kB is the Boltzmann constant (1.3810-23 J/K). hc/kB = 1.44 cm K
5.33 Lecture Notes: Principles of Molecular Spectroscopy

Low T Ni

High T kTlow kThigh Ei

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At room temperature (300 K), kBT/hc = 208 cm-1. This means that energy states near or below 200 cm-1 will have thermal population at room temperature. These are typically only rotational states in the ground vibrational and ground electronic state.

2)

Transition dipole moment

The strength of the transition is dictated by the change in the dipole moment with coordinate.

Dipole moment selection rules!

a) b)

vibration Q Rotation requires polar molecule!

Quantum: Transition dipole moment. The probability of transition is

Pif =

* final

initial dr

= q i ri is dipole operator
i

Requires change of parity ( g u symmetry).

parallel to symmetry axis) Q

* v

q x vdx 0

if v = v 1

Anharmonic oscillator v relaxed.

* J,M J

q x J,M dx 0 if J

J = J 1

(MJ = 0)

(Together with vibrational transition with q to symmetry axis J = 1, 0, +1).

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