Infrared Spectroscopy and Optical Constants of Porous Amorphous Solid Water

Journal Article · Thu Apr 02 04:00:00 EDT 2009 · Journal of Physical Chemistry B, 113(13):4131-4140

DOI:https://doi.org/10.1021/jp806738a· OSTI ID:958441

Cholette, Francois; Zubkov, Tykhon; Smith, R Scott; Dohnalek, Zdenek; Kay, Bruce D; Ayotte, Patrick

Reflection-absorption infrared spectra (RAIRS) of amorphous solid water (ASW) films grown at 20K on a Pt(111) substrate at various incidence angle (θBeam = 0-85o) using a molecular beam are reported. They display complex features arising from the interplay between refraction, absorption within the sample, and interference effects between the multiple reflections at the film-substrate and film-vacuum interfaces. Using a simple classical optics model based on Fresnel equations, we obtain optical constants [i.e., n(ω) and k(ω)] for porous ASW in the 1000-4000cm-1 (10-2.5 μm) range. The behaviour of the optical properties of ASW in the intramolecular OH stretching region with increasing θBeam is shown to be strongly correlated with its decreasing density and increasing surface area. A direct comparison between the RAIRS and calculated vibrational spectra shows a large difference (~200cm-1) in the position of the coupled H-bonded intramolecular OH stretching vibrations spectral feature. Moreover, this band shifts in opposite directions with increasing θBeam in RAIRS and vibrational spectra demonstrating RAIRS spectra cannot be interpreted straightforwardly as vibrational spectra due to severe optical distortions from refraction and interference effects.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 958441
• Report Number(s): PNNL-SA-61796; 24694; KC0301020
• Journal Information: Journal of Physical Chemistry B, 113(13):4131-4140, Journal Name: Journal of Physical Chemistry B, 113(13):4131-4140 Journal Issue: 13 Vol. 113
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AMORPHOUS STATE
DENSITY
Environmental Molecular Sciences Laboratory
FILMS
ICE
INFRARED SPECTRA
MATHEMATICAL MODELS
OPTICAL PROPERTIES
PLATINUM
SUBSTRATES
SURFACE AREA
VIBRATIONAL STATES