Infrared photodissociation spectroscopy

Infrared photodissociation–mass spectrometry

FT-ICR system

Acronym| IRPD
Classification| Infrared Spectroscopy
Mass spectrometry
Analytes| ion clusters
organic molecules
biomolecules
Other techniques
Related| Spectroscopy

Infrared photodissociation (IRPD) spectroscopy uses infrared radiation to break bonds in, often ionic, molecules (photodissociation), within a mass spectrometer.[1] In combination with post-ionization, this technique can also be used for neutral species. IRPD spectroscopy has been shown to use electron ionization, corona discharge, and electrospray ionization to obtain spectra of volatile and nonvolatile compounds.[2][3] Ionized gases trapped in a mass spectrometer can be studied without the need of a solvent as in infrared spectroscopy.[4]

Schematic diagram of infrared photodissociation spectrometer

## Contents

* 1 History
* 2 Instrumentation
* 3 Application
* 4 References

## History

Scientists began to wonder about the energetic of cluster formation early in the 19th century. Henry Eyring developed the activated-complex theory describing kinetics of reactions.[5] Interest in studying the weak interactions of molecules and ions(e.g. van der Waals) in clusters encouraged gas phase spectroscopy, in 1962 D.H. Rank studied weak interactions in the gas phase using traditional infrared spectroscopy.[6] D.S. Bomse used IRPD with an ICR to study isotopic compounds in 1980 at California Institute of Technology.[7] Spectroscopy for weak bonding clusters was limited by low cluster concentration and the variety of accessible cluster states.[8] Cluster states vary in part due to frequent collisions with other species, to reduce collisions in gas phase IRPD forms clusters in low pressure ion traps (e.g. FT-ICR). Nitrogen and water were one of the first complexes studied with the aid of a mass spectrometer by A. Good at University of Alberta in the 1960s.[9][3]

## Instrumentation

Photodissociation is used to detect electromagnetic activity of ions, compounds, and clusters when spectroscopy cannot be directly applied. Low concentration of analyte is usually the critical and inhibiting factor to measure absorption in the gas phase.[4] Mass spectrometers, e.g., time-of-flight and ion cyclotron resonance, have been used to study hydrated ion clusters.[10] Instruments are able to use ESI to effectively form hydrated ion clusters. Laser ablation and corona discharge have also been used to form ion clusters. Complexes are directed through a mass spectrometer where they are irradiated with infrared light, Physics:Nd:YAG laser.[10]

## Application

Infrared photodissociation spectroscopy maintains a powerful capability to study bond energies of coordination complexes. IRPD can measure varying bond energies of compounds, including dative bonds and coordination energies of molecular clusters.[1][3] Structural information about analytes can acquired by using mass selectivity and interpreting fragmentation. The spectroscopic information usually resembles that of linear infrared spectra and can be used to obtain detailed structural information of gas-phase species, in case of metal complexes, insights into ligand coordination, bond activations and successive reactions can be obtained.[11]

## References

1. ↑ 1.0 1.1 Lepetit, Christine; Maraval, Valérie; Canac, Yves; Chauvin, Remi (2016-02-01). "On the nature of the dative bond: Coordination to metals and beyond. The carbon case". Coordination Chemistry Reviews. Perspectives in Coordination Chemistry on the Occasion of the 40th anniversary of the LCC-CNRS, Toulouse, France 308, Part 2: 59–75. doi:10.1016/j.ccr.2015.07.018.
2. ↑ Oh, Han-Bin; Lin, Cheng; Hwang, Harold Y.; Zhai, Huili; Breuker, Kathrin; Zabrouskov, Vladimir; Carpenter, Barry K.; McLafferty, Fred W. (2005-03-01). "Infrared Photodissociation Spectroscopy of Electrosprayed Ions in a Fourier Transform Mass Spectrometer". Journal of the American Chemical Society 127 (11): 4076–4083. doi:10.1021/ja040136n. ISSN 0002-7863. PMID 15771545.
3. ↑ 3.0 3.1 3.2 Niedner-Schatteburg, Gereon; Bondybey, Vladimir E. (2000). "FT-ICR Studies of Solvation Effects in Ionic Water Cluster Reactions" (in en). Chemical Reviews 100 (11): 4059–4086. doi:10.1021/cr990065o. PMID 11749340.
4. ↑ 4.0 4.1 Walker, Nicholas R.; Walters, Richard S.; Duncan, Michael A. (2005-11-22). "Frontiers in the infrared spectroscopy of gas phase metal ion complexes" (in en). New Journal of Chemistry 29 (12): 1495. doi:10.1039/B510678H. ISSN 1369-9261.
5. ↑ McQuarrie, Donald (1997). Physical Chemistry : a molecular approach. Sausalito, CA: University Science Books. pp. 1165. ISBN 978-0935702996.
6. ↑ Rank, D. H. (1962-12-01). "Absorption Spectra of Hydrogen‐Halide—Rare Gas Mixtures". The Journal of Chemical Physics 37 (11): 2511–2515. doi:10.1063/1.1733048. ISSN 0021-9606. Bibcode: 1962JChPh..37.2511R.
7. ↑ Bomse, D.S. (January 1981). "Infrared photochemistry of (CH3)2Cl+, (CH3)Cl+ (CD3) and (CD3)2Cl+ in the gas phase using low-intensity cw laser radiation" (in en). Chemical Physics Letters 77 (1): 25–29. doi:10.1016/0009-2614(81)85592-3. Bibcode: 1981CPL....77...25B.
8. ↑ Miller, R. E. (1986-07-01). "Infrared laser photodissociation and spectroscopy of van der Waals molecules". The Journal of Physical Chemistry 90 (15): 3301–3313. doi:10.1021/j100406a003. ISSN 0022-3654.
9. ↑ Good, A.; Durden, D. A.; Kebarle, P. (1970). "Ion–Molecule Reactions in Pure Nitrogen and Nitrogen Containing Traces of Water at Total Pressures 0.5–4 torr. Kinetics of Clustering Reactions Forming H+(H2O)n" (in en). The Journal of Chemical Physics 52 (1): 212–221. doi:10.1063/1.1672667. Bibcode: 1970JChPh..52..212G.
10. ↑ 10.0 10.1 Metz, Ricardo B. (2004-07-01). "Optical spectroscopy and photodissociation dynamics of multiply charged ions". International Journal of Mass Spectrometry 235 (2): 131–143. doi:10.1016/j.ijms.2004.04.009. Bibcode: 2004IJMSp.235..131M. https://zenodo.org/record/1473785.
11. ↑ Fielicke, André (2023). "Probing the binding and activation of small molecules by gas-phase transition metal clusters via IR spectroscopy" (in en). Chemical Society Reviews 52 (11): 3778–3841. doi:10.1039/D2CS00104G. ISSN 0306-0012. http://xlink.rsc.org/?DOI=D2CS00104G.

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