Electron detachment photodetachment

Anion photoelectron spectroscopy [37, 38] amd photodetachment techniques [39] provide accurate information on electron detachment energies of negative ions. Ten closed-shell ainions considered here exhibit sharp peaks, indicative of minor or vanishing final-state nuclear rearrangements, in their photoelectron spectra. Comparisons between theory and experiment are straiightforward, for differences between vertical and adiabatic electron detachment energies (VEDEs and AEDEs, respectively) are small. 

Electron detachment from anionic mono-, di-, and trinucleotides was studied experimentally by electrospray photodetachment photoelectron spectroscopy (EPPS) [74]. Substrates did not decompose at the relatively low temperatures of these experiments. 

The behavior of CTTS states is dependent on energy levels of the ion-solvent molecular couphngs. These levels can lead to internal relaxation and/or complete electron detachment via adiabatic or nonadiabatic electron transfer. The ultrafast spectroscopic investigations of electronic dynamics in ionic solutions would permit us to learn more about the primary steps of an electron-transfer reaction within a cationic atmosphere. The influence of counterions on early electron photodetachment trajectories from a hahde ion can be considered as prereactive steps of an electron transfer. 

The continuous spectrum is also present, both in physical processes and in the quantum mechanical formalism, when an atomic (molecular) state is made to interact with an external electromagnetic field of appropriate frequency and strength. In conjunction with energy shifts, the normal processes involve ionization, or electron detachment, or molecular dissociation by absorption of one or more photons, or electron tunneling. Treated as stationary systems with time-independent atom - - field Hamiltonians, these problems are equivalent to the CESE scheme of a decaying state with a complex eigenvalue. For the treatment of the related MEPs, the implementation of the CESE approach has led to the state-specific, nonperturbative many-electron, many-photon (MEMP) theory [179-190] which was presented in Section 11. Its various applications include the ab initio calculation of properties from the interaction with electric and magnetic fields, of multiphoton above threshold ionization and detachment, of analysis of path interference in the ionization by di- and tri-chromatic ac-fields, of cross-sections for double electron photoionization and photodetachment, etc. 

Photodetachment spectroscopy of negative ions like IHI- and similar systems, studied by Neumark and coworkers (Metz, Kitsopoulos, Weaver, and Neumark 1988 Weaver, Metz, Bradforth, and Neumark 1988 Metz et al. 1990 Bradforth et al. 1990 Neumark 1990 Weaver and Neumark 1991) has provided the first conclusive manifestation of reactive resonances for a purely repulsive PES. The idea of the experiment goes as follows a photon with frequency u detaches the electron from the negative ion producing e- and IHI. If the PES for the neutral molecule is dissociative, the IHI complex subsequently breaks apart into I and HI. 

Sofar the imaging results of Fig. 3.1 were discussed in very classical terms, using the notion of a set of trajectories that take the electron from the atom to the detector. However, this description does not do justice to the fact that atomic photoionization is a quantum mechanical proces. Similar to the interference between light beams that is observed in Young s double slit experiment, we may expect to see the effects of interference if many different quantum paths exist that connect the atom to a particular point on the detector. Indeed this interference was previously observed in photodetachment experiments by Blondel and co-workers, which revealed the interference between two trajectories by means of which a photo-detached electron can be transported between the atom and the detector [33]. The current case of atomic photoionization is more complicated, since classical theory predicts that there are an infinite number of trajectories along which the electron can move from the atom to a particular point on the detector [32,34], Nevertheless, as Fig. 3.2 shows, the interference between trajectories is observable [35] when the resolution of the experiment is improved [36], The number of interference fringes smoothly increases with the photoelectron energy. 

Electrons can be released from negative ions, either by photodetachment or by collisional detachment ... 

The total photodetachment cross section describes the probability that an electron is detached from a negative ion following the absorption of a photon, regardless the excitation state of the residual atom or the energy or direction of the emitted electron. A total cross section is the sum of partial cross sections for detachment into each of the energetically allowed continua. This is illustrated in Fig. 1. Here we show the three possible channels accessible to a doubly excited state of Li" that lies just below the Li(32P) detachment threshold. The total cross section may be determined by... 

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