Infrared multiphoton dissociation
|Related||Blackbody infrared radiative dissociation
Electron capture dissociation
How it works
An infrared laser is directed through a window into the vacuum of the mass spectrometer where the ions are. The mechanism of fragmentation involves the absorption by a given ion of multiple infrared photons. The parent ion becomes excited into more energetic vibrational 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. A model proposed by Talebpour et al. explains this mechanism as the following.
- Multiphoton ionization (MPI) of electrons from the inner orbitals of the molecule which results in a molecular ion in ro-vibrational levels of an excited electronic state;
- Rapid radiationless transition to the high-lying ro-vibrational levels of a lower electronic state;
- Subsequent dissociation of the ion to different fragments through various fragmentation channels.
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 IRMPD 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.
- Infrared spectroscopy
- Tandem mass spectrometry
- Blackbody infrared radiative dissociation
- Electron capture dissociation
- Collision-induced dissociation is another, more common, method to fragment gas phase ions.
- 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 separate 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.
- Little DP, Speir JP, Senko MW, O'Connor PB, McLafferty FW (1994). "Infrared multiphoton dissociation of large multiply charged ions for biomolecule sequencing". Anal. Chem. 66 (18): 2809–15. doi:10.1021/ac00090a004. PMID 7526742.
- Talebpour et al., Multiphoton ionization of inner-valence electrons and fragmentation of ethylene in an intense Ti:sapphire laser pulse, 1999, Chemical Physics Letters, 313, 789–794
- Talebpour et al., Dissociative ionization of benzene in intense ultra-fast laser pulses, 2000, J. Phys. B: At. Mol. Opt. Phys. 33 4615
- Laskin J, Futrell JH (2005). "Activation of large ions in FT-ICR mass spectrometry". Mass spectrometry reviews 24 (2): 135–67. doi:10.1002/mas.20012. PMID 15389858.
- Polfer, Nick C.; Oomens, J (2007). "Reaction products in mass spectrometry elucidated with infrared spectroscopy". Physical Chemistry Chemical Physics 9 (29): 3804–17. Bibcode:2007PCCP....9.3804P. doi:10.1039/b702993b. PMID 17637973.
- Gruene P, Rayner DM, Redlich B, van der Meer AFG, Lyon JT, Meijer G, Fielicke A (2008). "Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase". Science 321 (5889): 674–6. Bibcode:2008Sci...321..674G. doi:10.1126/science.1161166. PMID 18669858.