A scheme of matrix ionization in UV matrix-assisted laser desorptiodionization is presented. Excitation to an upper lying electronic singlet state by the absorption of two photons and subsequent thermionic emission by vibronic coupling is proposed as the primary route for the formation of unprotonat
A quantitative model of ultraviolet matrix-assisted laser desorption/ionization
โ Scribed by R. Knochenmuss
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 218 KB
- Volume
- 37
- Category
- Article
- ISSN
- 1076-5174
- DOI
- 10.1002/jms.349
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โฆ Synopsis
Abstract
A quantitative model of primary ionization in ultraviolet matrixโassisted laser desorption/ionization (UVโMALDI) is presented. It includes not only photochemical processes such as exciton pooling, but also the effects of the desorption event. The interplay of these two is found to be a crucial aspect of the MALDI process. The desorbing plume is modeled as an adiabatic expansion with entrained clusters. The parameters in the model are defined as much as possible via experiment or by analogy with known effects. The model was applied to the matrix 2,5โdihydroxybenzoic acid and found to reproduce the fluence dependence of the fluorescence yield and key features of the picosecond twoโpulse ion generation efficiency curves. In addition, the model correctly predicts a fluence rather than irradiance threshold, the magnitude of the threshold, the magnitude of the ion yield, laser wavelength effects, plume temperatures, plume expansion velocities and the spot size effect. Copyright ยฉ 2002 John Wiley & Sons, Ltd.
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