Journal of Physical Chemistry, Vol.100, No.19, 7797-7809, 1996
Dispersed Fluorescence-Spectrum of Acetylene from the (A)over-Tilde (1)A(U) Origin - Recognition of Polyads and Test of Multiresonant Effective Hamiltonian Model for the (X)over-Tilde State
We have recorded a high-resolution dispersed fluorescence (DF) spectrum of the (A) over tilde (1)A(u) --> (X) over tilde (1) Sigma(g)(+) transition of acetylene-h(2), utilizing the zero-point level of the (A) over tilde (1)A(u) state, Here we present only the analysis of the vibrational levels of the (X) over tilde-state with E(vib) < 10 000 cm(-1). By comparing the observed and calculated spectral intensity patterns, we have estimated the previously undetermined pure bend vibrational constant, s(45)(h2), to be -11(2) cm(-1). Unlike previously recorded DF spectra, this DF spectrum is uniquely suited for comparison with an effective Hamiltonian since (1) the Franck-Condon envelope facilitates observation of levels at lower E(vib) in the (X) over tilde-state, (2) the improved resolution is sufficient to observe intramolecular vibrational redistribution (IVR) at lower E(vib), and (3) spectral features are no longer absent because of nodal patterns in the Franck-Condon envelope. Our comparison shows that our current effective Hamiltonian model, (H) over cap(eff)(R), can qualitatively describe the IVR pathways on the (X) over tilde-state for chromostates (zero-order bright states) which contain high excitation in the trans-bend (upsilon(4) less than or equal to 12). The failure of our (H) over cap(eff)(R) model for chromostates which contain excitation in both the CC stretch (upsilon(2)) and the trans-bend (upsilon(4) > 8) may be attributed to a new stretch-bend or stretch-only resonance. Comparison of the present DF spectrum to prior SEP spectra has allowed us to make plausible rotational and vibrational assignments for previously unassigned transitions in the SEP spectra.
Keywords:HIGHLY EXCITED ACETYLENE;APPROXIMATE CONSTANTS;VIBRATIONAL LEVELS;ENERGY;ROTATION;SYSTEMS;MOTION