Isolation of stable intermediates in reactive gas mixtures: Rotational spectrum of H3P...Cl2 in a pulsed jet

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Abstract
The weakly bound dimer H3P...Cl2 has been isolated in a pulsed jet by keeping the highly reactive components H3P and Cl2 separate until the point at which they expand into the evacuated Fabry–Pérot cavity of a pulsed-nozzle Fourier-transform microwave spectrometer. The rotational spectra of the three symmetric-top isotopomers H3P...35Cl 35Cl, H3P...35Cl 37Cl, and H3P...37Cl 35Cl detected in this way have been analyzed to give the ground-state spectroscopic constants B0, DJ, DJK, χ1(Cl), and χ2(Cl). Comparison of the dimer properties determined from the spectroscopic constants of H3P...Cl2 with those of the hydrogen-bonded dimer H3P...HCl indicates that charge transfer is not predominant in the interaction of PH3 and Cl2. Some parallels in the properties of B...Cl2 and B...HCl are discussed for B=PH3 and HF.