Epf. Lee et al., SIMULATION OF EMISSION-SPECTRA OF THE PF2 (B-2(2)-]X(2)B(1)) TRANSITION BY AB-INITIO CALCULATION AND FRANCK-CONDON ANALYSIS, Journal of physical chemistry, 100(51), 1996, pp. 19795-19800
Geometry optimization and harmonic vibrational frequency calculations
were carried out on the X(2)B(1) and the lowest B-2(2) states of PF2 a
t the MP2/6-31G and MP2/6-311G(2df) levels. CCSD(T)/6-311G(2df)//MP2/
6311G(2df) calculations were also performed to obtain improved adiabat
ic and vertical transition energies for the two combining electronic s
tates. In addition, Frandk-Condon analyses were carried out employing
the ab initio data obtained to simulate emission spectra of the PF2(B-
2(2) --> X(2)B(1)) transition. Both the computed relative energies and
the theoretical spectra confirm that the observed emission spectra by
Zhao and Setser were due to the B-2(2) --> X(2)B(1) transition. Furth
ermore, the geometry of PF2 in the lowest B-2(2) state was also varied
in the vibrational intensity calculations to give the best agreement
between the theoretical and observed spectra. The bond length and bond
angle thus deduced for PF2 in the B-2(2) state are 1.628 +/- 0.008 An
gstrom and 84.9 +/- 0.2 degrees, respectively. Spectra involving excit
ed vibrational levels of the B-2(2) State were also generated by assum
ing the Boltzmann distribution at selected temperatures. Comparison of
these spectra with the observed one suggested that the vibrational po
pulation distribution in the upper state does not follow the Boltzmann
rule. The potential surface of the upper B-2(2) state under study may
be perturbed vibronically by that of the lower, near-linear, (2)A(1)
state via the asymmetric stretching mode. This may explain why the the
oretical spectra as obtained using the harmonic oscillator model are d
ifferent from the experimental one.