Multiphoton-Ionization-Mass Spectrometry (MUPI-MS) [New Analytical Methods (34)]

Mass spectrometry is one of the most important analytical tools in chemistry, biology, medicine and related areas. During the past 30 years, methods have been developed, both for the qualitative as well as the quantitative analysis of a wide variety of substances. The introduction of lasers into chemistry has also profited mass spectrometry, since its nonlinear properties and its tunability open up fundamentally new frontiers. Multiphoton ionization mass spectrometry combines UV-spectroscopy and mass spectrometry, thus providing a two-dimensional method that enables substance-specific and even state-specific analyses. This progress report presents the fundamentals and possibilities of MUPI mass spectrometry and discusses investigations on amino acids, peptides, chlorophylls and sugars. For each substance, multiphoton ionization can be tuned in such a way that only the molecular ion is formed. An increase of laser intensity induces substance-specific fragmentations of the molecule, thus contributing to a quick and easy identification of the substance.     

Fragmentation reactions of some aliphatic esters in the NCl(F−) and NCl(NH2−) mass spectra

The NCI(F^?) and NCI(NH₂^?) mass spectra of a series of aliphatic acetates and of methyl and ethyl trimethylacetate have been obtained. The formation of fluoroenolate ions CH₂COF^? and of carboxamide anions RCONH^? (R ? CH₃))CH₃C). respectively, is observed besides formation of [M ? H]^? ions and carboxylate ions RCOO^? (R ? CH₃, (CH₃)₃C). The relative intensities of the different anions depend on the structure of the ester molecules and on the primary reactant anions. Usually, the NCI(NH₂^?) spectra of the acetates are dominated by [M ? H]^? ions ([M? D]^? ions in the case of trideuteroacetates) fragmenting unimolecularly by elimination of an alcohol. The carboxylate ions are important fragments, too, but carboxamide ions are only observed with large intensities in the NCI(NH₂^? spectra of the trimethylacetates. The NCI(F^?) spectra show much larger intensities of carboxylate ions and fluoroenolate ions. The mechanisms of the fragmentation reactions are discussed. The results indicate that most or even all of the fragment ions in the NCI(F^? mass spectra of aliphatic esters are formed by addition-elimination reactions via a tetrahedral intermediate, while competition between direct proton abstraction and addition-elimination reactions occurs in the NCI(NH₂^?) mass spectra because of the higher basicity of NH₂^? resulting in an early transition state for direct proton abstraction.     

Laser-induced electron impact ionization in a reflectron time-of-flight mass spectrometer

Some details of the generation of electrons by impinging a laser beam on a metal surface are described. It is shown that highly efficient electron generation is observed only during the laser pulse. Therefore, this technique delivers intense pulses of electrons. The process is investigated and different ion source set-ups are discussed. In conjunction with a time-of-flight mass spectrometer this technique can be used to produce mass spectra of different samples ranging from simple organic molecules to peptides.     

13C labelling study of the interconversion of ethylbenzene, 7-methylcycloheptatriene and p-xylene ions

The isomerization of the molecular ions of ethylbenzene, 7-methylcycloheptatriene and p-xylene by skeletal rearrangement prior to the formation of [C₇H₇]⁺ ions has been investigated by using ¹³C labelled compounds. The results obtained for ions generated by 70 eV and 12 eV electron impact, and fragmenting in the ion source, the 1st field free region and the 2nd field free region, respectively, are compared with those obtained from D labelled derivatives. It is shown that at long reaction times metastable p-xylene ions lose a methyl radical after scrambling of all C atoms and H atoms, while the unstable molecular ions in the ion source react by specific loss of one of the methyl substituents. Both unstable and metastable ethylbenzene ions fragment by two competing mechanisms, one corresponding to specific loss of the terminal methyl group, and the other involving scrambling of all C and H atoms. These results are discussed by use of a dynamic model developed for the mutual interconversion and fragmentation of the molecular ions of ethylbenzene, methylcyclo-heptatriene and p-xylene. The experimental results can be explained by an equilibrium between metastable methylcycloheptatriene ions and p-xylene ions with sufficient energy for skeletal rearrangement, while about 40% of the metastable ethylbenzene ions fragment after rearrangement to methylcycloheptatriene ions and about 60% of the ethylbenzene ions rearrange further to xylene ions before fragmentation. Metastable methylcycloheptatriene ions, mainly lose a methyl group without a skeletal rearrangement, however, because the rearranged ions are kinetically trapped as ‘stable’ xylene ions or ethylbenzene ions.     

Inconsistency in the application of the adiabatic theorem

The adiabatic theorem states that an initial eigenstate of a slowly varying Hamiltonian remains close to an instantaneous eigenstate of the Hamiltonian at a later time. We show that a perfunctory application of this statement is problematic if the change in eigenstate is significant, regardless of how closely the evolution satisfies the requirements of the adiabatic theorem. We also introduce an example of a two-level system with an exactly solvable evolution to demonstrate the inapplicability of the adiabatic approximation for a particular slowly varying Hamiltonian.     

The physical meaning of Fermi coordinates

Fermi coordinates (FC) are supposed to be the natural extension of Cartesian coordinates for an arbitrary moving observer in curved space-time. Since their construction cannot be done on the whole space or even in the whole past of the observer we examine which construction principles are responsible for this effect and how they may be modified. A proposal for a modification is made and applied to the observer with constant acceleration in the two- and four-dimensional Minkowski space. The two-dimensional case shows some surprising similarities to Kruskal space which generalize those found by Rindler for the outer region of Kruskal space and the Rindler wedge. In perturbational approaches the modification also leads to different predictions for certain physical systems. As an example we consider atomic interferometry and derive the deviation of the acceleration-induced phase shift from the standard result in Fermi coordinates.     

Photodissociation mass spectra and mass-selected resonant (1+1)-photodissociation spectroscopy of some alkyl iodide radical cations

Photodissociation (PD) mass spectra and mass selected (1+1)-photodissociation spectra of C(2)H(5)I(+?), C(2)D(5)I(+?),1- C(3)H(7)I(+?), 2-C(3)H(7)I(+?), 1-C(4)H(9)I(+?) and 2- C(4)H(9)I(+?) radical cations were studied within the ? ← X~ absorption band. The photodissociation mass spectra within the range 13,600-15,900 cm(-1) (1.68-1.97 eV) evidence only a simple cleavage of the C-I bond and formation of the corresponding alkyl ions. The resonant (1+1)-photodissociation spectra of C(2)H(5)I(+?) and C(2)D(5)I(+?) show intense vibrational structure in the excited ? state. The thresholds for formation of the states of C(2)H(5)I(+?) and C(2)D(5)I(+?) were estimated to be (13,278 ± 12) cm(-1) (1.6462 ± 0.0014 eV)and (13,363 ± 12) cm(-1) (1.6586 ± 0.0014 eV), respectively. Whereas a few resonant vibronic excitations could be identified with 1-C(3)H(7)I(+?) and 1- C(4)H(7)I(+), no vibrational features were observable with 2- C(3)H(7)I(+?) and 2-C(4)H(9)I(+?). It is concluded that 1- and 2-iodoalkane radical cations do not rearrange, even under the conditions of electron ionisation used to generate the molecular ions.