Related Experiment Video
Updated: Jul 19, 2026

Infrared Degenerate Four-wave Mixing with Upconversion Detection for Quantitative Gas Sensing
Published on: March 22, 2019
Near-infrared spectroscopy of H3+ above the barrier to linearity
1Department of Chemistry, University of Chicago, Chicago, IL 60637, USA. jennifer.gottfried@arl.army.mil
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.
Related Concept Videos
IR Frequency Region: X–H Stretching
IR Frequency Region: Fingerprint Region
The...
IR Spectrum Peak Broadening: Hydrogen Bonding
However, the extent of hydrogen bonding influences the observed stretching frequency and band broadening. Intermolecular or intramolecular hydrogen bonding...
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are slanted or...
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration
According to Hooke's law, the vibrational frequency is directly proportional to the...
IR and UV–Vis Spectroscopy of Aldehydes and Ketones

