# 13: Molecular Spectroscopy

Spectroscopy generally is defined as the area of science concerned with the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules, which may be in the gas, liquid, or solid phase. Visible electromagnetic radiation is called light, although the terms light, radiation, and electromagnetic radiation can be used interchangeably. Spectroscopy played a key role in the development of quantum mechanics and is essential to understanding molecular properties and the results of spectroscopic experiments. It is used as a “stepping stone” to take us to the concepts of quantum mechanics and the quantum mechanical description of molecular properties in order to make the discussion more concrete and less abstract and mathematical.

- 13.1: The Electromagnetic Spectrum
- Electromagnetic radiation—light—is a form of energy whose behavior is described by the properties of both waves and particles. Some properties of electromagnetic radiation, such as its refraction when it passes from one medium to another are explained best by describing light as a wave. Other properties, such as absorption and emission, are better described by treating light as a particle.

- 13.2: Rotations Accompany Vibrational Transitions
- Below, will learn how the rotational transitions of molecules can accompany the vibrational transitions. It is important to know how each peak correlates to the molecular processes of molecules. Rovibrational spectra can be analyzed to determine average bond length.

- 13.3: Unequal Spacings in Vibration-Rotation Spectra
- As molecules are excited to higher rotational energies they spin at a faster rate. The faster rate of spin increases the centrifugal force pushing outward on the molecules resulting in a longer average bond length. Looking back, B and l are inversely related. Therefore the addition of centrifugal distortion at higher rotational levels decreases the spacing between rotational levels.

- 13.4: Unequal Spacings in Pure Rotational Spectra
- Vibrational energy which is a consequence of the oscillations/ vibrations of the nuclei along inter nuclear axis, is possible only when the distance between the nuclei is not fixed/ rigid; that means the separation between the two nuclei is flexible/ elastic (non-rigid rotator). Consequently, centrifugal force, when the molecule is rotating, tends to fly the reduced mass μ away from the axis of rotation. To keep the mass rotating about the axis, there must be some restoring force to counter bal

- 13.5: Vibrational Overtones
- Combination bands, overtones, and Fermi resonances are used to help explain and assign peaks in vibrational spectra that do not correspond with known fundamental vibrations. Combination bands and overtones generally have lower intensities than the fundamentals. Hot bands will also be briefly addressed.

- 13.6: Electronic Spectra Contain Electronic, Vibrational, and Rotational Information
- Molecules can also undergo changes in electronic transitions during microwave and infrared absorptions. The energy level differences are usually high enough that it falls into the visible to UV range; in fact, most emissions in this range can be attributed to electronic transitions.

- 13.7: The Franck-Condon Principle
- The Franck-Condon Principle describes the intensities of vibronic transitions, or the absorption or emission of a photon. It states that when a molecule is undergoing an electronic transition, such as ionization, the nuclear configuration of the molecule experiences no significant change. This is due in fact that nuclei are much more massive than electrons and the electronic transition takes place faster than the nuclei can respond. When the nucleus realigns itself with with the new electronic c

- 13.8: Rotational Spectra of Polyatomic Molecules
- To consider the rotational energy of molecules, it is useful to divided molecules into five categories: Diatomic, linear, symmetric tops, spherical tops, and asymmetric tops. The principle moments of inertial of polyatomic molecules: Rotation of the molecule can take places about any axis passing through the center of mass. There are two unique axes that are at 90º of each other, and about which the moment of inertia is a minimum or a maximum.

- 13.9: Normal Modes in Polyatomic Molecules
- Normal modes are used to describe the different vibrational motions in molecules. Each mode can be characterized by a different type of motion and each mode has a certain symmetry associated with it. Group theory is a useful tool in order to determine what symmetries the normal modes contain and predict if these modes are IR and/or Raman active. Consequently, IR and Raman spectroscopy is often used for vibrational spectra.

- 13.10: Irreducible Representation of Point Groups
- Each of these coordinates belongs to an irreducible representation of the point the molecule under investigation. Vibrational wavefunctions associated with vibrational energy levels share this property as well. The normal coordinates and the vibration wavefunction can be categorized further according to the point group they belong to. From the character table predictions can be made for which symmetries can exist.

- 13.11: Time-Dependent Perturbation Theory
- Time-dependent perturbation theory, developed by Paul Dirac, studies the effect of a time-dependent perturbation V(t) applied to a time-independent Hamiltonian. Since the perturbed Hamiltonian is time-dependent, so are its energy levels and eigenstates. Thus, the goals of time-dependent perturbation theory are slightly different from time-independent perturbation theory.

- 13.12: The Selection Rule for the Rigid Rotor
- A selection rule describes how the probability of transitioning from one level to another cannot be zero. This presents a selection rule for rigid rotors that transitions are forbidden for Δl=0.

- 13.13: The Harmonic Oscillator Selection Rule
- Transitions with Δv= ±1, ±2, ... are all allowed for anharmonic potential, but the intensity of the peaks become weaker as Δv increases. v=0 to v=1 transition is normally called the fundamental vibration, while those with larger Δv are called overtones. Δv=0 transition is allowed between the lower and upper electronic states with energy E1 and E2 are involved, i.e. (E1, v''=n) →→ (E2, v'=n), where the double prime and prime indicate the lower and upper quantum state.

- 13.14: Group Theory Determines Infrared Activity
- Group theory makes it easy to predict which normal modes will be IR and/or Raman active. If the symmetry label of a normal mode corresponds to x, y, or z, then the fundamental transition for this normal mode will be IR active. If the symmetry label of a normal mode corresponds to products of x, y, or z (such as \(x^2\) or yz) then the fundamental transition for this normal mode will be Raman active.

- 13.E: Molecular Spectroscopy (Exercises)
- These are exercises for Chapter 13 of the McQuarrie and Simon Textmap for Physical Chemistry.