Radiative lifetimes optical double resonance

Radford (1961, 1962) and Radford and Broida (1962) presented a complete theory of the Zeeman effect for diatomic molecules that included perturbation effects. This led to a series of detailed investigations of the CN B2E+ (v — 0) A2II (v = 10) perturbation in which many of the techniques of modern high-resolution molecular spectroscopy and analysis were first demonstrated anticrossing spectroscopy (Radford and Broida, 1962, 1963), microwave optical double resonance (Evenson, et at, 1964), excited-state hyperfine structure with perturbations (Radford, 1964), effect of perturbations on radiative lifetimes and on inter-electronic-state collisional energy transfer (Radford and Broida, 1963). A similarly complete treatment of the effect of a magnetic field on the CO a,3E+ A1 perturbation complex is reported by Sykora and Vidal (1998). The AS = 0 selection rule for the Zeeman Hamiltonian leads to important differences between the CN B2E+ A2II and CO a/3E+ A1 perturbation plus Zeeman examples, primarily in the absence in the latter case of interference effects between the Zeeman and intramolecular perturbation terms. 

For transitions between sublevels in the ground state, the radiative lifetimes may be extremely long and the linewidth is only limited by the transit time of the molecules through the RF field. Sub-kilohertz resonances have been observed in the RF-optical double resonance spectroscopy of rare-earth ions [519]. 

If the intermediate state has a reasonably long radiative lifetime, of the order of 10 -10 s, it is possible to achieve a sufficient population of the intermediate state such that ON lasers can be used for the multistep excitation processes. This approach, with CW lasers, has been used for optical-optical double resonance (OODR) studies, one of the earliest examples being a study of the EOg ion-pair state of I2. The excitation scheme used was as follows ... 

We have shown in previous chapters that the -values of spectral lines are important fundamental data which must be known before detailed calculations of the behaviour of gas discharges, plasmas, or stellar atmospheres can be undertaken. Since it is difficult, in many cases, to make theoretical calculations of f-values to an accuracy of better than 20 per cent, experimental measurements of these quantities are essential. A considerable number of different techniques have been developed for this purpose, many of them involving the determination of radiative lifetimes. In this chapter we discuss two such techniques, namely the beam-foil and the delayed-coincidence methods. In Chapter 8 we shall discuss the determination of the f-values of resonance lines by studies of the profiles of spectral lines and in Chapters 15 and 16 the use of the Hanle effect and optical double resonance methods. 

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