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Abstract

First-principles computations and experimental measurements of transition energies are carried out for vibrational overtone lines of the triatomic hydrogen ion H₃⁺ corresponding to floppy vibrations high above the barrier to linearity. Action spectroscopy is improved to detect extremely weak visible-light spectral lines on cold trapped H₃⁺ ions. A highly accurate potential surface is obtained from variational calculations using explicitly correlated Gaussian wave function expansions. After nonadiabatic corrections, the floppy H₃⁺vibrational spectrum is reproduced at the 0.1  cm^-1 level up to 16 600  cm^-1.