Title: Ultraviolet spectroscopy of pressurized and supercritical carbon dioxide

Journal Article · · Communications Chemistry
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Abstract Carbon dioxide (CO 2 ) is prevalent in planetary atmospheres and sees use in a variety of industrial applications. Despite its ubiquitous nature, its photochemistry remains poorly understood. In this work we explore the density dependence of pressurized and supercritical CO 2 electronic absorption spectra by vacuum ultraviolet spectroscopy over the wavelength range 1455-2000 Å. We show that the lowest absorption band transition energy is unaffected by a density increase up to and beyond the thermodynamic critical point (137 bar, 308 K). However, the diffuse vibrational structure inherent to the spectrum gradually decreases in magnitude. This effect cannot be explained solely by collisional broadening and/or dimerization. We suggest that at high densities close proximity of neighboring CO 2 molecules with a variety of orientations perturbs the multiple monomer electronic state potential energy surfaces, facilitating coupling between binding and dissociative states. We estimate a critical radius of ~4.1 Å necessary to cause such perturbations.

Research Organization:
Univ. of Notre Dame, IN (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
FC02-04ER15533
OSTI ID:
1784582
Journal Information:
Communications Chemistry, Journal Name: Communications Chemistry Journal Issue: 1 Vol. 4; ISSN 2399-3669
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United Kingdom
Language:
English

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