Spectra of CO2-Rg2 and CO2-Rg-He trimers (Rg = Ne, Ar, Kr, and Xe): intermolecular CO2 rock, vibrational shifts and three-body effects

TL;DR

This study uses high-resolution infrared spectroscopy to analyze the vibrational spectra and structural parameters of CO2-Rg2 and CO2-Rg-He trimers, revealing subtle shifts and three-body effects across different rare gas atoms.

Contribution

It extends previous spectroscopic analysis of CO2-Rg2 trimers to include Ne, Kr, and Xe, providing new vibrational shift data and structural insights, as well as spectra of mixed CO2-Rg-He trimers.

Findings

Trimer vibrational shifts are slightly more positive than dimer extrapolations.

Intermolecular CO2 rock vibrational mode values are approximately 32-35 cm-1.

Structural parameters of CO2-Rg2 trimers are compared with dimers, revealing three-body effects.

Abstract

Weakly-bound CO2-Rg2 trimers are studied by high resolution (0.002 cm-1) infrared spectroscopy in the region of the CO2 nu3 fundamental band (~2350 cm-1), using a tunable OPO to probe a pulsed supersonic slit jet expansion with an effective rotational temperature of about 2 K. CO2-Ar2 spectra have been reported previously, but are extended here to include Rg = Ne, Kr, and Xe as well as new combination and hot bands. For Kr and Xe, a unified scaled parameter scheme is used to account for the many possible isotopic species. Vibrational shifts of CO2-Rg2 trimers are compared to those of CO2-Rg dimers, and in all cases the trimer shifts are slightly more positive (blue-shifted) than expected on the basis of linear extrapolation from the dimer. Combination bands directly measure an intermolecular vibrational mode (the CO2 rock), and gives values of about 32.2, 33.8, and 34.7 cm-1 for CO2-Ar2, -Kr2, and -Xe2. Structural parameters derived for CO2-Rg2 trimers are compared with those of CO2-Rg and Rg2 dimers. Spectra of the mixed trimers CO2-Rg-He are also reported.