High-Sensitivity Raman Spectrometer To Study Pristine and Irradiated Interstellar Ice Analogs

• Published in: Analytical chemistry (Washington) 2013-06, Vol.85 (12), p.5659-5665
• Main Authors: Bennett, Chris J, Brotton, Stephen J, Jones, Brant M, Misra, Anupam K, Sharma, Shiv K, Kaiser, Ralf I
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Bands; Carbon dioxide; Carbon Dioxide - analysis; Carbon monoxide; Design engineering; Fourier transforms; Ice; Ice - analysis; Infrared; Irradiation; Molecules; Raman spectroscopy; Spectrometers; Spectroscopy; Spectroscopy, Fourier Transform Infrared - methods; Spectrum analysis; Spectrum Analysis, Raman - methods
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac303259y

We discuss the novel design of a sensitive, normal-Raman spectrometer interfaced to an ultra-high vacuum chamber (5 × 10–11 Torr) utilized to investigate the interaction of ionizing radiation with low temperature ices relevant to the solar system and interstellar medium. The design is based on a pulsed Nd:YAG laser which takes advantage of gating techniques to isolate the scattered Raman signal from the competing fluorescence signal. The setup incorporates innovations to achieve maximum sensitivity without detectable heating of the sample. Thin films of carbon dioxide (CO2) ices of 10 to 396 nm thickness were prepared and characterized using both Fourier transform infrared (FT-IR) spectroscopy and HeNe interference techniques. The ν+ and ν– Fermi resonance bands of CO2 ices were observed by Raman spectroscopy at 1385 and 1278 cm–1, respectively, and the band areas showed a linear dependence on ice thickness. Preliminary irradiation experiments are conducted on a 450 nm thick sample of CO2 ice using energetic electrons. Both carbon monoxide (CO) and the infrared inactive molecular oxygen (O2) products are readily detected from their characteristic Raman bands at 2145 and 1545 cm–1, respectively. Detection limits of 4 ± 3 and 6 ± 4 monolayers of CO and O2 were derived, demonstrating the unique power to detect newly formed molecules in irradiated ices in situ. The setup is universally applicable to the detection of low-abundance species, since no Raman signal enhancement is required, demonstrating Raman spectroscopy as a reliable alternative, or complement, to FT-IR spectroscopy in space science applications.