Spin-orbit interaction and Renner-Teller effect in HCCCCH studied by high-resolution photoelectron spectroscopy.

The photoelectron spectra of the XΠ ← X Σ photoionizing transition of diacetylene (HCCCCH) and d2-diacetylene (DCCCCD) have been recorded at high resolution using the technique of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy. The partially resolved rotational structure of the origin band of the spectra of HCCCCH and DCCCCD has enabled the determination of the adiabatic ionization energies of HCCCCH [E = 82072.2(5) cm] and DCCCCD [E = 82090.0(10) cm] and of the spin-orbit coupling constant [A = -31.1(4) cm] of the ground vibronic state of HCCCCH, which is smaller than the value of -33.3 cm commonly used since the work of Callomon (J. H. Callomon, Can. J. Phys., 1956, 34, 1046). Several excited vibrational levels of HCCCCH and DCCCCD, including some affected by the Renner-Teller effect and Fermi interactions, have been observed and the fundamental wavenumber of the mode ν has been determined in both HCCCCH (200.0(10) cm) and DCCCCD (192.6(20) cm). Possible assignments for several of these levels are discussed and deficiencies in the current understanding of the energy-level structure of the radical cation of diacetylene are pointed at.