Abstract
Gas-phase ion spectroscopy requires specialised apparatus, both when it comes to measuring photon absorption and light emission (fluorescence). The reason is much lower ion densities compared to solution-phase spectroscopy. In this chapter different setups are described, all based on mass spectrometry and many of them home-built: electrostatic ion storage devices, accelerator mass spectrometers (i.e., sector instruments), reflectron time-of-flight mass spectrometers, and ion traps. The experimental results presented in this volume were obtained with such instruments. Detection schemes are detailed, both for the identification of neutral products and charged ones. In delayed dissociation experiments, prompt dissociation is a problem as all the fragmentation is then not sampled; an example is photo-induced electron transfer to an ammonium group and subsequent hydrogen loss. A way to circumvent this is discussed based on a chemical approach, namely tagging of ammonium groups by crown ether. Prompt dissociation can sometimes be identified from the total beam depletion differing from that due to statistical dissociation. Special emphasis in this chapter is on the limitations and pitfalls in data interpretation, and the advantages and disadvantages of the different techniques are clarified. New instrumental developments involving cryo-cooled storage rings, which show great promise for the future, are briefly touched upon.
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Wyer, J.A. (2013). Experimental Techniques. In: Brøndsted Nielsen, S., Wyer, J. (eds) Photophysics of Ionic Biochromophores. Physical Chemistry in Action. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-40190-9_3
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