화학공학소재연구정보센터
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.