Question

In: Chemistry

Describe the types of transition a molecule could undergo, giving typical energies values of such transitions...

Describe the types of transition a molecule could undergo, giving typical energies values of such transitions and identifying the regions of the spectrum responsible for initiating these transitions.

Solutions

Expert Solution

Electrons in atoms and molecules can change (make transitions in) energy levels by emitting or absorbing a photon(of electromagnetic radiation) whose energy must be exactly equal to the energy difference between the two levels. Electrons can also be completely removed from a chemical species such as an atom, molecule, or ion. Complete removal of an electron from an atom can be a form of ionization, which is effectively moving the electron out to anorbital with an infinite principal quantum number, in effect so far away so as to have practically no more effect on the remaining atom (ion). For various types of atoms, there are 1st, 2nd, 3rd, etc. ionization energies for removing the 1st, then the 2nd, then the 3rd, etc. of the highest energy electrons, respectively, from the atom originally in theground state. Energy in corresponding opposite quantities can also be released, sometimes in the form of photon energy, when electrons are added to positively charged ions or sometimes atoms. Molecules can also undergo transitions in their vibrational or rotational energy levels. Energy level transitions can also be nonradiative, meaning emission or absorption of a photon is not involved.

If an atom, ion, or molecule is at the lowest possible energy level, it and its electrons are said to be in the ground state. If it is at a higher energy level, it is said to be excited, or any electrons that have higher energy than the ground state are excited. Such a species can be excited to a higher energy level byabsorbing a photon whose energy is equal to the energy difference between the levels. Conversely, an excited species can go to a lower energy level by spontaneously emitting a photon equal to the energy difference. A photon's energy is equal to Planck's constant (h) times its frequency (ν) and thus is proportional to its frequency, or inversely to its wavelength (λ).

ΔE = h ν = h c / λ,

since c, the speed of light, equals to ν λ

Correspondingly, many kinds of spectroscopy are based on detecting the frequency or wavelength of the emitted or absorbed photons to provide information on the material analyzed, including information on the energy levels and electronic structure of materials obtained by analyzing the spectrum.

An asterisk is commonly used to designate an excited state. An electron transition in a molecule's bond from a ground state to an excited state may have a designation such as σ → σ*, π → π*, or n → π* meaning excitation of an electron from a σ bonding to a σ antibonding orbital, from a π bonding to a π antibonding orbital, or from an n non-bonding to a π antibonding orbital. [3][4] Reverse electron transitions for all these types of excited molecules are also possible to return to their ground states, which can be designated as σ* → σ, π* → π, or π* → n.

A transition in an energy level of an electron in a molecule may be combined with a vibrational transition and called a vibronic transition. A vibrational and rotational transition may be combined by rovibrational coupling. In rovibronic coupling, electron transitions are simultaneously combined with both vibrational and rotational transitions. Photons involved in transitions may have energy of various ranges in the electromagnetic spectrum, such as X-ray, ultraviolet, visible light, infrared, or microwave radiation, depending on the type of transition. In a very general way, energy level differences between electronic states are larger, differences between vibrational levels are intermediate, and differences between rotational levels are smaller, although there can be overlap. Translational energy levels are practically continuous and can be calculated as kinetic energy using classical mechanics.


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