State-selective/specific methods

Luntz and co-workers have recently carried out an impressive study that follows in the spirit of the Eley-Rideal work.44 Specifically, laser-assisted recombination of N-atoms desorbing to form gas-phase N2 on Ru(0001) was investigated. Experimental measurements of state-selectively detected N2 recoiling from the surface recombination event were obtained using resonance enhanced multiphoton ionization and ion time-of-flight methods. In this way translational energy distributions of individual rovibrational states could be obtained experimentally. In addition, N2-vibrational population distributions could be derived. 

Although multidimensional separation generally offers enhanced selectivity and discrimination of solutes, application of more than one hyphenated techniques is usually required for complete and unequivocal identification of the analytes. A recent report states that two widespread misconceptions about mass spectroscopy (MS) are that GC-MS is a specific method and tlrat GC-MS is 100% accurate (5). The 1989 Forensic Urine Drug Confirmation Study by the American Association for Clinical Chemistry/College of American Pathologists confirmed this concern about overreliance on GC-MS as a confirmation method (5). 

For the assessment of the contribution of the emission categories to the observed NMVOC concentrations the Chemical Mass Balance (CMB) modelling technique, version 8 from United States Environmental Protection Agency (Watson et al., 1998 Watson et al., 2001) was selected. The method uses source specific ratios between the emission rates of certain set of compounds and aims to recognise these fingerprints, or soiuce profiles, in the profile measured at the receptor point. As a result the CMB model delivers contributions from each source type to the total ambient NMVOC and individual hydrocarbon species at receptor points and their uncertainties. 

For these and other reasons, much attention was given to the so-called state-selective or state-specific (SS) MR CC approaches. These are basically of two types (i) essentially SR CCSD methods that employ MR CC Ansatz to select a subset of important higher-than-pair clusters that are then incorporated either in a standard way [163,164], or implicitly [109-117], or via the so-called externally corrected (ec) approaches of either the amplimde [214-219] or energy [220,221] type, and (ii) those actually exploiting Bloch equations, but focusing on one state at a time [222]. The energy-correcting ec CC approaches [220,221] are in fact very closely related to the renormalized CCSD(T) method of Kowalski and Piecuch mentioned earlier [146,147]. 

In gas-phase dynamics, the discussion is focused on the TD quantum wave packet treatment for tetraatomic systems. This is further divided into two different but closed related areas molecular photofragmentation or half-collision dynamics and bimolecular reactive collision dynamics. Specific methods and examples for treating the dynamics of direct photodissociation of tetraatomic molecules and of vibrational predissociation of weakly bound dimers are given based on different dynamical characters of these two processes. TD methods such as the direct projection method for direct photodissociation, TD golden rule method and the flux method for predissociation are presented. For bimolecular reactive scattering, the use of nondirect product basis and the computation of the initial state-selected total reaction probabilities by flux calculation are discussed. The descriptions of these methods are supported by concrete numerical examples and results of their applications. 

As input, this model requires the standard state chemical potentials (or free energies) AfG° of all species and phases, and the bulk composition or total number of moles of each component, Bg. A specific method must always be selected to calculate activity coefficient corrections. 

Most of the available data have been obtained for reactants which are not state-selected and the important role of internal excitation energy is becoming increasingly apparent (Section 3.6.1). A major emphasis must now be given to establishing the reliability of these data. While reactant ion production by electron impact is unsatisfactory because it is not specific, important methods have been developed to analyze the distribution of electronic... 

The product state distribution can be measured directly, for example by laser induced fluorescence (LIF) or resonance enhanced multiphoton ionisation (REMPI). Both of these techniques yield the quantum specific density of AB molecules that are created in the dissociation process. However, these methods can be applied only to a limited number of molecules. Whereas LIF is essentially restricted to a few diatomic molecules, REMPI allows in a few favoured cases also the state selective detection of larger molecules. 

State of the precursor neutral, the final photon absorption process often occurs from a specific vibrational state of the neutral to an ion with the same vibrational quantum number. Under such conditions, vibrational state selection can be achieved by multiphoton absorption. The method has been applied successfully in the production of NH cations with specific excitation in the V2 umbrella-bending mode. 

Other analytical techniques. Electroanalytical methods can also be used to differentiate between ionic species (based on valence state) of the same element by selective reduction or oxidization. In brief, the electroanalytical methods measure the effect of the presence of analyte ions on the potential or current in a cell containing electrodes. The three main types are potentiometry, where the voltage difference between two electrodes is determined, coulometry, which measures the current in the cell over time, and voltammetry, which shows the changes in the cell current when the electric potential is varied (current-voltage diagrams). In a recent review article, 43 different EA methods for measuring uranium were mentioned and that literature survey found 28 voltammetric, 25 potentiometric, 5 capillary electrophoresis, and 3 polarographic methods (Shrivastava et al. 2013). Some specific methods will be discussed in detail in the relevant chapters of this tome. 

---