Near-infrared spectroscopy of above the barrier to linearity

Abstract

Since the Royal Society Discussion Meeting on H3+ in 2000, the laboratory spectroscopy of H3+ has entered a new regime. For the first time, transitions of H3+ above the barrier to linearity have been observed. A highly sensitive near-infrared spectrometer based on a titanium:sapphire laser and incorporating a dual-beam, double-modulation technique with bidirectional optical multi-passing has been developed in order to detect these transitions, which are more than 4600 times weaker than the fundamental band. We discuss our recent work on the 2v1 + 2v2(2) <-- 0, 3v1 + v2(1) <-- 0, v1 + 4v2(2) <-- 0, v1 + 4V2(4) <-- 0 and 2v1 + 3v2(1) <-- 0 combination bands and the 5v2(1) <-- 0, 5v2(3) <-- 0, 52(5) <-- 0 and 6v2(2) <-- 0 overtone bands. Experimentally determined energy levels provide a critical test of ab initio calculations in this challenging energy regime (greater than 10,000 cm(-1)). By comparing the experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated, the extent of higher-order effects such as non-adiabatic and radiative corrections is revealed.