Jt. Farrell et al., PAIRWISE AND NONPAIRWISE ADDITIVE FORCES IN WEAKLY-BOUND COMPLEXES - HIGH-RESOLUTION INFRARED-SPECTROSCOPY OF ARNDF (N=1,2,3), The Journal of chemical physics, 103(7), 1995, pp. 2395-2411
High resolution infrared spectra of the v(DF)=1 <-- 0 stretch in ArnDF
(n = 1-3) have been recorded using a slit-jet infrared spectrometer.
Analysis of the rotationally resolved spectra provides vibrationally a
veraged geometries and vibrational origins for a DF chromophore sequen
tially ''solvated'' by Ar atoms. Calculations using pairwise additive
Ar-Ar and Ar-DF potentials predict lowest energy equilibrium structure
s consistent with the vibrationally averaged geometries inferred spect
roscopically. Variational calculations by Ernesti and Hutson [A. Ernes
ti and J. M. Hutson, Faraday Discuss. Chem. Soc. (1994)] using pairwis
e additive potentials predict rotational constants which are in qualit
ative agreement with, but consistently larger than, the experimental v
alues. The inclusion of nonpairwise additive (three-body) terms improv
es the agreement, though still not to within the uncertainty of the pa
ir potentials. The vibrational redshifts of 8.696, 11.677, and 14.461
cm(-1) for n=1-3, respectively, reflect a nonlinear dependence of the
redshift on the number of Ar atoms. Both the variational calculations
of Ernesti and Hutson and diffusion quantum Monte Carlo calculations [
M. Lewerenz, J. Chem. Phys. (in press)] using pairwise additive potent
ials systematically overpredict the magnitude of these redshifts, furt
her signifying the need for corrective three-body terms. Analysis of t
he ArnDF (n=2,3) rovibrational line shapes reveals an upper limit to h
omogeneous broadening on the order of 2-3 MHz, consistent with vibrati
onal predissociation lifetimes in excess of 50 ns. (C) 1995 American I
nstitute of Physics.