Infrared Multiphoton Dissociation
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Infrared multiple photon dissociation (IRMPD) is a technique used in
mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is used ...
to fragment molecules in the gas phase usually for structural analysis of the original (parent) molecule.


How it works

An
infrared Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those ...
laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word ''laser'' originated as an acronym for light amplification by stimulated emission of radi ...
is directed through a window into the
vacuum A vacuum (: vacuums or vacua) is space devoid of matter. The word is derived from the Latin adjective (neuter ) meaning "vacant" or "void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressur ...
of the
mass spectrometer Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a '' mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is us ...
where the ions are. The mechanism of fragmentation involves the absorption by a given ion of multiple
infrared Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those ...
photon A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless particles that can ...
s. The parent ion becomes excited into more energetic
vibration Vibration () is a mechanical phenomenon whereby oscillations occur about an equilibrium point. Vibration may be deterministic if the oscillations can be characterised precisely (e.g. the periodic motion of a pendulum), or random if the os ...
al states until a bond(s) is broken resulting in gas phase fragments of the parent ion. In the case of powerful laser pulses, the dissociation proceeds via inner-valence ionization of electrons. IRMPD is most often used in Fourier transform ion cyclotron resonance mass spectrometry.


Infrared photodissociation spectroscopy

By applying intense tunable IR lasers, like IR- OPOs or IR free electron lasers, the wavelength dependence of the IRMPD yield can be studied. This infrared photodissociation spectroscopy allows for the measurement of vibrational spectra of (unstable) species that can only be prepared in the gas phase. Such species include molecular ions but also neutral species like metal clusters that can be gently ionized after interaction with the IR light for their mass spectrometric detection.


Analytical applications

The combination of mass spectrometry and IRMPD with tunable lasers (IR ion spectroscopy) is increasingly recognized as a powerful tool for small-molecule identification. Examples are metabomics, where biomarkers are identified in body fluids (urine, blood, cerebrospinal) and forensic sciences, where isomeric designer drugs were identified in seized samples.


Isotope separation

Due to the relatively large differences in IR absorption frequencies that are due to different resonance frequencies for molecules containing different isotopes, this technique has been suggested as a way to perform
Isotope separation Isotope separation is the process of concentrating specific isotopes of a chemical element by removing other isotopes. The use of the nuclides produced is varied. The largest variety is used in research (e.g. in chemistry where atoms of "marker" n ...
with difficult-to-separate isotopes, in a single pass. For example, molecules of UF6 containing U-235 might be ionized completely as a result of such a laser resonance, leaving UF6 containing the heavier U-238 intact.


See also

*
Infrared spectroscopy Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functio ...
* Tandem mass spectrometry *
Photodissociation Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by absorption of light or photons. It is defined as the interaction of one or more photons wi ...
* Blackbody infrared radiative dissociation * Electron capture dissociation *
Collision-induced dissociation Collision-induced dissociation (CID), also known as collisionally activated dissociation (CAD), is a mass spectrometry technique to induce fragmentation (chemistry), fragmentation of selected ions in the gas phase. The selected ions (typically m ...
is another, more common, method to fragment gas phase ions.


References

{{mass spectrometry Tandem mass spectrometry Measuring instruments