Resonant excitation multiphoton ionization

In contrast to the ionization of C q after vibrational excitation, typical multiphoton ionization proceeds via the excitation of higher electronic levels. In principle, multiphoton ionization can either be used to generate ions and to study their reactions, or as a sensitive detection technique for atoms, molecules, and radicals in reaction kinetics. The second application is more common. In most cases of excitation with visible or UV laser radiation, a few photons are enough to reach or exceed the ionization limit. A particularly important teclmique is resonantly enlianced multiphoton ionization (REMPI), which exploits the resonance of monocluomatic laser radiation with one or several intennediate levels (in one-photon or in multiphoton processes). The mechanisms are distinguished according to the number of photons leading to the resonant intennediate levels and to tire final level, as illustrated in figure B2.5.16. Several lasers of different frequencies may be combined. 

Nitrosobenzene was studied by NMR and UV absorption spectra at low temperature146. Nitrosobenzene crystallizes as its dimer in the cis- and fraws-azodioxy forms, but in dilute solution at room temperature it exists only in the monomeric form. At low temperature (—60 °C), the dilute solutions of the dimers could be obtained because the thermal equilibrium favours the dimer. The only photochemistry observed at < — 60 °C is a very efficient photodissociation of dimer to monomer, that takes place with a quantum yield close to unity even at —170 °C. The rotational state distribution of NO produced by dissociation of nitrosobenzene at 225-nm excitation was studied by resonance-enhanced multiphoton ionization. The possible coupling between the parent bending vibration and the fragment rotation was explored. 

The vibration spectrum of the first excited state of guanine was measured using laser desorption jet-cooled resonance-enhanced multiphoton ionization (REMPI) spectrometry <1999JA4896>. The millimeter wave spectrum of purine was collected using a free jet spectrometer, and the observed rotational spectrum was assigned to the N(9)-H tautomer <1996CPL189>. 

Photolysis of the dimer, reaction (44), proceeds primarily via generation of Cl + ClOO (Cox and Hayrnan, 1988 Molina et al., 1990). For example, Molina et al. (1990) reported the quantum yield for this channel at 308 nm to be unity, with an uncertainty of 30%. Okumura and co-workers (Moore et al., 1999) and Schindler and co-workers (Schmidt et al., 1998) have reported that the quantum yield is less than 1.0. For example, Schmidt et al. (1998) used resonance-enhanced multiphoton ionization (REMPI) with time-of-flight (TOF) mass spectrometry to follow the production of oxygen and chlorine atoms as well as CIO in vibrational levels up to v" = 5 in the photolysis of the dimer. At a photolysis wavelength of 250 nm, the quantum yield for chlorine atom production was measured to be 0.65 + 0.15, but CIO was not observed. Assuming that all of the excited dimer dissociates, this suggests that the production of CIO in vibrational... 

Resonance-enhanced multiphoton ionization (REMPI) has proved to be a versatile ionization technique for MS offering a number of advantageous features in the field of chemical analysis. Since it makes use of substance-specific excited states for the ionization process, it involves UV spectroscopy of the molecule to be ionized. Thus, it enables ionization of preselected compounds, control of the degree of fragmentation and, for a large number of substances, a high ionization efficiency. These features require that the excited molecular state(s) involved in the REMPI process not be significantly depleted... 

An attempt to establish the role of exciplexes in a reactive system was made by Kendler and Haas [27]. The fluorescence characteristics of the styrene-trimethylamine (TMA) adduct were studied in a supersonic jet. In the bulk, this system is known to exhibit exciplex emission and also to form photoproducts [42]. In the jet, fluorescence excitation of the STY-TMA 1 1 adduct revealed two isomers, an R-type and an E-type (Figure 9) (labeled n-type and w-type, respectively, in the original paper). The resonance-enhanced multiphoton ionization (REMPl)... 

Using 2-photon excitation and 1+1 resonance-enhanced multiphoton ionization detection, Sha and co-workers (Sha, et al., 1995, Chen, et al., 1996) have measured cross-sections for CO A1n(u == 0) —> e3E (v = 1) transitions. The transition rates were found to be enhanced at spectroscopic perturbations between these vibronic levels and, moreover, displayed interference effects similar to those displayed in calculations on CaO collisions, described below. 

In addition to laser fluorescence excitation, several other laser spectroscopic methods have been found to be useful for the state-selective and sensitive detection of products of reactive collisions resonance-enhanced multiphoton ionization [58], coherent anti-Stokes Raman scattering [M], bolometric detection with laser excitation [30], and direct infrared absorption [7]. Several additional laser techniques have been developed for use in spectroscopic studies or for diagnostics in reacting systems. Of these, four-wave mixing [ ] is applicable to studies of reaction dynamics although it does have a somewhat lower sensitivity than the techniques mentioned above. 

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