Journal of Chemical Physics, Vol.109, No.22, 9762-9771, 1998
The first electronic states of Ar-2(+) studies by high resolution photoelectron spectroscopy
The pulsed-field-ionization (PFI) zero-kinetic-energy (ZEKE) photoelectron spectrum of Art has been recorded between 116500 cm(-1) and 128200 cm(-1). The spectrum consists of a long progression of transitions to the vibrational levels of the ground A (2)Sigma(1/2u)(+), State of Ar-2(+) with v(+) up to 52, a shorter progression of four bands attributed to transitions to the first. four vibrational levels of the C (2)Pi(1/2u) state and of a single sharp line assigned to the C (2)Pi(3/2u)(v(+) = 0) <-- X (1)0(g)(+)(v = 0) transition. Rotational constants of several vibrational levels of the A (2)Sigma(1/2u)(+) state have been determined from high resolution PFI-ZEKE photoelectron spectra. From these measurements new information on the first electronic states of Ar-2(+) has been extracted. An analytical potential energy function has been derived for the A (2)Sigma(1/2u)(+) state which extends to large internuclear distances (beyond 5 Angstrom) and reproduces all measured vibrational energy levels up to v(+) = 52. The adiabatic ionization potential for the photoelectronic transitions to the A (2)Sigma(1/2u)(+), C (2)Pi(3/2u) and C (2)Pi(1/2u) states are determined to be 116591.1 +/- 6 cm(-1), 126883.9 +/- 3 cm(-1) and 128004.1 +/- 5 cm(-1), respectively, from which dissociation energies (D-0(+)) of 10603.7 +/- 6 cm(-1), 310.8 +/- 3 cm(-1), and 622.5 +/- 5 cm(-1) are obtained. The vibrational levels of the C (2)Pi(1/2u) state can be described by a Morse potential with w(e) = 58.9 +/- 0.8 cm(-1) and w(e)x(e) = 1.40 +/- 0.27 cm(-1), respectively. Associative ionization and collisional ionization processes involving argon atom Rydberg states induce spurious peaks in the PFI-ZEKE photoelectron spectrum. Ways to unambiguously identify these spurious peaks are discussed.
Keywords:RARE-GAS DIMERS, VACUUM-UV REGION, POTENTIAL-ENERGY CURVES;THRESHOLD PHOTOELECTRON, ABSORPTION SPECTRUM, EMISSION-SPECTRUM, ARGON DIMER, IONS, IONIZATION, MOLECULE