Time resolved photoionization

In several studies, we have combined TRPD data with results obtained over a broader energy range by the time-resolved photoionization mass spectrometer (TPIMS) technique of Lifshitz s group," which is not fully energy resolved but provides a successful complementary technique to TRPD, as shown in the examples below. 

We have investigated the vibrational relaxation of Na3F by time-resolved photoionization at the threshold. Among the two isomers of Na3F, we have studied the excited electronic states of the C2v one. The pump-probe signal clearly shows damped oscillations, the period of which is fitted to 390 8 fs, close to twice the previously measured bending mode of Na2F,[l] while the relaxation time is 1275 50 fs. 

D. R. Cyr and C. C. Hayden, /. Chem. Phys., 104,771 (1996). Femtosecond Time-Resolved Photoionization and Photoelectron-Spectroscopy Studies of Ultrafast Internal Conversion in 1,3,5-Hexatriene. 

Middaugh, J.E. (2014) The Study of Bimolecular Radical Reactions Using a Novel Time-resolved Photoionization Time-of-flight Mass Spectrometry and Laser Absorption Spectrometry Apparatus. PhD Thesis, Massachusetts Institute of Technology. 

The simplest signal to be measured in a time-resolved photoionization experiment is the total ion yield following the action of pump and probe pulses. It is given by the integral population of the ionization continua in the limit t —> oo. ... 

When considering the femtosecond photoionization dynamics of complex systems, a completely exact evaluation of the time and energy resolved photoelectron spectrum is often not really necessary. Approximative schemes which require significantly lower computational effort are valuable in such cases. Within the nonperturbative formalism, Meier et al. have proposed an efficient computational scheme which incorporates the multi-configuration time-dependent Hartree method.An approximate method which is based on a classical-trajectory description of the nuclear dynamics has been elaborated by Hartmann, Heidenreich, Bonacic-Koutecky and coworkers and applied, among other systems,to the time-resolved photoionization spectroscopy of conical intersections in sodium fluoride clusters. 

Slow dissociation rates (10 -10 s ) have been measured in Dunbar s laboratory by time-resolved photodissociation, which consists of trapping ions in an ICR cell during a variable delay time after a phot-odissociating photon pulse. The technique called time-resolved photoionization mass spectrometry , developed by Lifshitz, consists of trapping photoions in a cylindrical trap at very low pressure to avoid bimolecular collisions, and then ejecting them into a mass filter after a variable delay covering the microsecond to millisecond range. When the dissociation rate constant becomes lower than ca. 10 s competition with infrared fluorescence takes place and limits the lifetime of the decomposition process. This has to be taken into account to extract the dissociation rate constant from the experimental data. 

Malinovich Y, and Lifshitz C (1986) Time-dependent mass spectra and breakdown graphs. 7. Time-resolved photoionization mass spectrometry of iodobenzene. The heat of formation of CeHs- Journal of Physical Chemistry 90 2200-2203. Malinovich Y and Llifshitz C (1986) Time-dependent mass spectra and breakdown graphs. 8. Dissociative photoionization of phenol. Journal of Physical Chemistry 90 4311-4317. 

A qualitatively different approach to probing multiple pathways is to interrogate the reaction intermediates directly, while they are following different pathways on the PES, using femtosecond time-resolved pump-probe spectroscopy [19]. In this case, the pump laser initiates the reaction, while the probe laser measures absorption, excites fluorescence, induces ionization, or creates some other observable that selectively probes each reaction pathway. For example, the ion states produced upon photoionization of a neutral species depend on the Franck-Condon overlap between the nuclear configuration of the neutral and the various ion states available. Photoelectron spectroscopy is a sensitive probe of the structural differences between neutrals and cations. If the structure and energetics of the ion states are well determined and sufficiently diverse in... 

Mass spectrometric studies are not limited to the investigation of stable intermediates they have also been carried out on reaction transition states. The ultrafast studies by Zewail, for example, are nominally mass spectrometric based, where photoionization is used to detect reactive species on exceedingly short (femtosecond) time scales.Time resolved studies provide insight into the rates of unimo-lecular reactions, but do not provide direct thermochemical insight. 

Recently, Zewail and co-workers have combined the approaches of photodetachment and ultrafast spectroscopy to investigate the reaction dynamics of planar COT.iii They used a femtosecond photon pulse to carry out ionization of the COT ring-inversion transition state, generated by photodetachment as shown in Figure 5.4. From the photoionization efficiency, they were able to investigate the time-resolved dynamics of the transition state reaction, and observe the ring-inversion reaction of the planar COT to the tub-like D2d geometry on the femtosecond time scale. Thus, with the advent of new mass spectrometric techniques, it is now possible to examine detailed reaction dynamics in addition to traditional state properties." ... 

Most of the theoretical work regarding the utility of time-resolved photoelectron angular distributions to probe electronic, vibrational, and rotational dynamics have also concerned neutral photoionization.(Adapted from Sanov, 2002)... 

Fig, 1. Pump-probe photoionization (PPI) and time-resolved degenrate four-wave mixing (TRDFWM) schemes for rotational coherence spectroscopy (RCS). 

Fig. 2. RCS of cyclohexylbenzene. Experimental data a) from pump-probe photoionization in a molecular beam (T 10 K) [2], b) from time-resolved degenerate four-wave mixing in a gas cell (T 305 K).

A further possibility is that the signals arise from hydrated electrons or base radical ions produced by monophotonic ionization of the polymers. However, the quantum yield for photoionization of adenosine is reported to be approximately the same as that of poly(A) and poly(dA) [25], It is unlikely that photoionization of the polymers can account for the signals seen here since there is no detectable signal contribution from the photoionization of single bases [4], The most compelling argument that our pump-probe experiments monitor excited-state absorption by singlet states is the fact that ps and ns decay components have been observed in previous time-resolved emission experiments on adenine multimers [23,26-28]. 

We turn now to a more detailed description of the photoionization probe step in order to clarify the ideas presented above. Time-resolved photoelectron spectroscopy probes the excited-state dynamics using a time-delayed probe laser pulse that brings about ionization of the excited-state wave packet, usually with a single photon... 

Photoionization always produces two species available for analysis the ion and the electron. By measuring both photoelectrons and photoions in coincidence, the kinetic electron may be assigned to its correlated parent ion partner, which may be identified by mass spectrometry. The extension of the photoelectron-photoion-coincidence (PEPICO) technique to the femtosecond time-resolved domain was shown to be very important for studies of dynamics in clusters [131, 132]. In these experiments, a simple yet efficient permanent magnet design magnetic bottle electron spectrometer was used for photoelectron... 

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