Ices in the interstellar medium largely exist as amorphous solids composed of small molecules including ammonia, water, and carbon dioxide. Describing gas-phase molecules can be readily accomplished with current high-level quantum chemical calculations with the description of crystalline solids becoming more readily accomplished. Differently, amorphous solids require more novel approaches. The present work describes a method for generating amorphous structures and constructing electronic spectra through a combination of quantum chemical calculations and statistical mechanics. The structures are generated through a random positioning program and DFT methods, such as ωB97-XD and CAM-B3LYP. A Boltzmann distribution weights the excitations to compile a final spectrum from a sampling of molecular clusters. Three ice analogs are presented herein consisting of ammonia, carbon dioxide, and water. Ammonia and carbon dioxide provide semi-quantitative agreement with experiment for CAM-B3LYP/6-311++G(2d,2p) from 30 clusters of 8 molecules. Meanwhile, the amorphous water description improves when the sample size is increased in cluster size and count to as many as 105 clusters of 32 water molecules. The described methodology can produce highly comparative descriptions of electronic spectra for ice analogs and can be used to predict electronic spectra for other ice analogs.
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The end of ice I
The appearance of ice I in the smallest possible clusters and the nature of its phase coexistence with liquid water could not thus far be unraveled. The experimental and theoretical infrared spectroscopic and free-energy results of this work show the emergence of the characteristic hydrogen-bonding pattern of ice I in clusters containing only around 90 water molecules. The onset of crystallization is accompanied by an increase of surface oscillator intensity with decreasing surface-to-volume ratio, a spectral indicator of nanoscale crystallinity of water. In the size range from 90 to 150 water molecules, we observe mixtures of largely crystalline and purely amorphous clusters. Our analysis suggests that the liquid–ice I transition in clusters loses its sharp 1st-order character at the end of the crystalline-size regime and occurs over a range of temperatures through heterophasic oscillations in time, a process without analog in bulk water.
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- Award ID(s):
- 1305427
- PAR ID:
- 10123873
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- 201914254
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.1914254116
