화학공학소재연구정보센터
Journal of Chemical Physics, Vol.108, No.2, 519-526, 1998
Near threshold photodissociation of acetylene
The photodissociation of jet-cooled HCCH molecules following excitation to their S-1 state has been investigated further, at a number of wavelengths in the range 205-220 nm, using the H atom photofragment translational spectroscopy (PTS) technique. Analysis of the rovibrational structure evident in the total kinetic energy release (TKER) spectra so obtained confirms previous reports that the resulting C2H((X) over tilde) fragments are formed in most (if not all) of the v(2) bending vibrational levels permitted by energy conservation, and that there is a clear preference for populating those states in which the axial projection of this vibrational angular momentum is maximized (i.e., states with l=v(2)) The distribution of ii atom recoil velocity vectors resulting from photolyses at the shorter excitation wavelengths (e.g., lambda(phot)=205.54nm) shows bimodal rotational distributions, and a marked anisotropy-especially in the case of those H atoms that are formed in association with C2H((X) over tilde) fragments carrying little rotational excitation. Two competing dissociations mechanisms have been identified. Our discussion of these observations is guided by the recent ab initio calculations of Cui and Morokuma [Chem. Phys. Lett. 272, 319 (1997)]. Channel I conforms to their proposal that the S-1 molecules reach the H+C2H((X) over tilde) asymptote as a result of sequential nonadiabatic couplings via the T-3, T-2, and T-1 potential energy surfaces. The product energy disposal at the longest excitation wavelengths is rationalized in terms of the forces acting as the dissociating molecule traverses a late barrier in the C-H exit channel on the T-1 surface, while the propensity for populating states with l=v(2) reflects the importance of parent torsional motion in promoting the S-1 --> T-3, T-3 --> T-2, and T-2 --> T-1 surface couplings. The population of low rotational states with high recoil anisotropy at shorter excitation wavelengths is ascribed to channel II, involving a direct nonadiabatic transition from S-1 to T-1 for a structure with one near linear CCH angle. In contrast to channel I, there is no extensive torsional motion and the anisotropy of the initial excitation is retained through to fragmentation. Excitation of the v(1)' mode of HCCH enhances the branching to channel II.