Line broadening transit-times

The Time Dependent Processes Seetion uses time-dependent perturbation theory, eombined with the elassieal eleetrie and magnetie fields that arise due to the interaetion of photons with the nuelei and eleetrons of a moleeule, to derive expressions for the rates of transitions among atomie or moleeular eleetronie, vibrational, and rotational states indueed by photon absorption or emission. Sourees of line broadening and time eorrelation funetion treatments of absorption lineshapes are briefly introdueed. Finally, transitions indueed by eollisions rather than by eleetromagnetie fields are briefly treated to provide an introduetion to the subjeet of theoretieal ehemieal dynamies. 

Once the basic work has been done, the observed spectrum can be calculated in several different ways. If the problem is solved in tlie time domain, then the solution provides a list of transitions. Each transition is defined by four quantities the mtegrated intensity, the frequency at which it appears, the linewidth (or decay rate in the time domain) and the phase. From this list of parameters, either a spectrum or a time-domain FID can be calculated easily. The spectrum has the advantage that it can be directly compared to the experimental result. An FID can be subjected to some sort of apodization before Fourier transfomiation to the spectrum this allows additional line broadening to be added to the spectrum independent of the sumilation. 

When collisions occur between gas phase atoms or molecules there is an exchange of energy, which leads effectively to a broadening of energy levels. If t is the mean time between collisions and each collision results in a transition between two states there is a line broadening Av of the transition, where... 

It is much more difficult to observe the Mossbauer effect with the 130 keV transition than with the 99 keV transition because of the relatively high transition energy and the low transition probability of 130 keV transition, and thus the small cross section for resonance absorption. Therefore, most of the Mossbauer work with Pt, published so far, has been performed using the 99 keV transition. Unfortunately, its line width is about five times larger than that of the 130 keV transition, and hyperfine interactions in most cases are poorly resolved. However, isomer shifts in the order of one-tenth of the line width and magnetic dipole interaction, which manifests itself only in line broadening, may be extracted reliably from Pt (99 keV) spectra. 

A source of line broadening which is fairly common in molecular beam studies, and often dominant in ion beam studies is transit time broadening. This arises when the interaction time between the electromagnetic radiation field and the molecule is limited by the time the molecule spends in the radiation field. The transit time t is equal to d/v, where v is the molecular velocity and d is the length of the radiation field. A typical... 

Among the numerous intrinsic causes of line broadening in the electronic spectra of large molecules, electronic relaxation (widely called radiationless transitions) is the most important and has received the greatest attention in recent times. 

Any discussion of nonradiative processes and line broadening must at some time make a reference to azulene. It is not our aim to review the wealth of spectroscopy that has been carried out on azulene over the past few years, but rather to describe some recent and very pertinent work by Hochstrasser and Li 48> on linewidths for the Si S0 (at 14652) and S2 S0 (at 28048 cm-1) transitions. The linewidths were measured at 1.2 K for azulene and azulene-ds in a naphthalene host crystal. 

The Spectrum of fig. 3 demonstrates the use of the spin echo to remove inhomogeneous line broadening and the use of time proportional phase increments (TPPI) to restore the offset. Resolution is limited by truncation of the multiple quantum free induction decay and scale of reproduction. The actual linewidth is less than 2 Hz for all orders and suffices to resolve all allowed transitions of all orders. 

In order to demonstrate the physical significance of asymjjtotic nonadiabatic transitions and especially the aiialj-tical theory developed an application is made to the resonant collisional excitation transfer between atoms. This presents a basic physical problem in the optical line broadening [25]. The theoretical considerations were mad( b( for< [25, 27, 28, 29, 25. 30] and their basic id( a has bec n verified experimentally [31]. These theoretical treatments assumed the impact parameter method and dealt with the time-dependent coupled differenticil equations imder the common nuclear trajectory approximation. At that time the authors could not find any analytical solutions and solved the coupled differential equations numerically. The results of calculations for the various cross sections agree well with each other and also with experiments, confirming the physical significance of the asymptotic type of transitions by the dipole-dipole interaction. 

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