The structures of fluorophosphane, PH2F, and
chlorophosphane, PH2Cl, have been calculated ab
initio at the
SCF, MP2, CCSD, and CCSD(T) levels using a quadruple ζ polarized
basis set. Equilibrium and ground state
rotational constants as well as centrifugal distortion constants have
been predicted for several isotopomers of
PH2F and PH2Cl. Theoretical
CCSD(T) geometries were also determined for the series of
PH
n
X3
-
n
(X = F, Cl;
n = 0−3) molecules using a triple ζ polarized basis
set. The millimeter-wave spectra of the short-lived
molecules
PH2F, PH2Cl, and their perdeuterated
species were measured in the frequency range 100−470 GHz. For
PH2F
and PH2Cl, accurate ground state parameters have been
obtained by a combined fit of the millimeter-wave data
and the infrared ground state combination differences. The
r
o, r
z, and
r
e structures of PH2F and
PH2Cl, as well
as PH3, PCl3, and PHF2 have been
determined. The experimental results are found in excellent
agreement with
their ab initio predictions.
The harmonic and anharmonic force fields of the title compounds have been calculated at the ab initio self-consistent-field level using effective core potentials and polarized double-zeta basis sets. Additional calculations for PH2F employ larger basis sets and include electron correlation. Many rovibrational constants are predicted theoretically. The infrared spectra generated from the ab initio data have guided the experimental identification of PH2F and PH2Cl in the gas phase. High resolution Fourier transform infrared spectra of these unstable molecules have been recorded for the first time. Rotational analyses for several bands are reported which provide accurate ground state constants and a precise characterization of a number of vibrationally excited states. The accuracy of the ab initio predictions for PH2F and PH2Cl is evaluated by comparisons with these experimental data.
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