Zeeman Effect, g Factors

In an earlier far-IR LMR study, gs and gf were held fixed at the free-electron (2.00232) and Curl (0.00455) values, and gR was allowed to vary in the fit which resulted in gR = -0.00072(39) [3]. 

The analysis of purely rotational, rotational-vibrational, and electronic spectra (cf. pp. 23/30) gave rotational and vibrational constants for the electronic ground state and various excited states of PH and PD. The more accurate values were obtained, of course, by IR Fourier transform and laser spectroscopy as compared to the conventional UV-visible spectroscopic methods (conventional IR spectroscopy has never been applied to PH). 

The electronic ground state X has been studied by far-IR [1 to 3] and mid-IR [4] laser magnetic resonance (LMR), diode laser absorption [7], and Fourier transform emission [6] spectroscopy as well as by analysis of the electronic spectrum [8]. The rotational constants Be or Bq, centrifugal distortion constants Dg or Dq, Hq, U, and the corresponding vibration-rotation interaction constants, tte, Ye, Pei K (where B = Be - tte(v +1 /2) + Ye(v +112) +... = De 

Theoretical values for the spectroscopic constants of PH were derived by polynomial fits of the potential curves which had been calculated from highly correlated ab initio wave functions. The results for the ground state and the lowest excited states reproduce the experimental results, and constants for the hitherto only tentatively assigned higher valence state d S ...(4a)2 (5a)° (2tc) were predicted. The extent of agreement between experiment and theory is demonstrated by the following compilation and a comparison with Tables 2 and 3 (Be, Bo, tte, (Oe, iti cnr in A)  

A number of further ab initio calculations [33 to 40] and one semiempirical (CNDO) study [41] dealt with geometry optimization for PH and predicted ground-state and, in one case [38], excited-state equilibrium internuclear distances. 

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Key words Photoluminescence, magneto-luminescence, Zeeman effect, g-factor, excitons, valence band symmetry... 

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