Morphology of Vapor-Deposited Acetonitrile Films

Tylinski, M.; Smith, R. Scott; Kay, Bruce D.

doi:10.1021/acs.jpca.0c03650

Morphology of Vapor-Deposited Acetonitrile Films

Journal Article · Tue Jul 07 00:00:00 EDT 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c03650· OSTI ID:1668331

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Crystalline acetonitrile has two polymorphs, a high temperature (HT) phase that is stable between 217 K and its melting point at 229 K, and a low temperature (LT) phase that is stable below 217 K. Solid acetonitrile films can be prepared by vapor deposition in an ultra-high vacuum chamber. To prevent sublimation of the film temperatures are often kept below 150 K. While the LT phase is thermodynamically favored at these low temperatures, such preparation usually results in the formation of the metastable HT polymorph. In this work we use reflection adsorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) experiments to investigate the effects of the deposition temperature and underlying substrate on the morphology of acetonitrile films prepared with molecular beam deposition. We obtained the elusive LT phase when dosing at 120 K on a graphene substrate and on a crystalline decane layer. Dosing acetonitrile on other surfaces produced the HT phase, as did annealing of amorphous films. We used TPD experiments to determine the Gibbs energy difference between the HT and LT phases. Our ΔG values agree with extrapolation of equilibrium calorimetry data. Furthermore, we also observed that acetonitrile films were amorphous when dosed at temperatures ≤ 60 K, and porous for temperatures ≤ 50 K.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1668331

Report Number(s):: PNNL-SA--152684

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 30 Vol. 124; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

New Millimeter Heterodyne Observations of Titan: Vertical Distributions of Nitriles HCN, HC3N, CH3CN, and the Isotopic Ratio 15N/14N in Its Atmosphere Marten, A. Icarus, Vol. 158, Issue 2 https://doi.org/10.1006/icar.2002.6897	journal	August 2002
Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C, N) species Sexton, B. A.; Avery, N. R. Surface Science, Vol. 129, Issue 1 https://doi.org/10.1016/0039-6028(83)90092-4	journal	June 1983
Interaction of acetonitrile with platinum (111): more properties of the η2(C,N) state and new species in the submonolayer Ou, E. C.; Young, P. A.; Norton, P. R. Surface Science, Vol. 277, Issue 1-2 https://doi.org/10.1016/0039-6028(92)90617-F	journal	October 1992
Raman spectra and phase transition of crystalline CH3CN and CD3CN Marzocchi, M. P.; Migliorini, M. G. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 29, Issue 8 https://doi.org/10.1016/0584-8539(73)80114-X	journal	August 1973
Infrared spectra and crystal structure of CH3CN and CD3CN. Polarization and intensity measurements Marzocchi, M. P.; Dobos, S. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 30, Issue 7 https://doi.org/10.1016/0584-8539(74)80151-0	journal	July 1974
The self-diffusivity of amorphous solid water near 150 K Smith, R. Scott; Dohnálek, Z.; Kimmel, Greg A. Chemical Physics, Vol. 258, Issue 2-3 https://doi.org/10.1016/S0301-0104(00)00130-0	journal	August 2000
Gas-phase deposition of acetonitrile: an attempt to understand Ostwald’s step rule on a molecular basis Tizek, Heinz; Grothe, Hinrich; Knözinger, Erich Chemical Physics Letters, Vol. 383, Issue 1-2 https://doi.org/10.1016/j.cplett.2003.11.014	journal	January 2004
Preparation, identification, and low-temperature infrared spectra of two elusive crystalline nitrile ices Hudson, Reggie L. Icarus, Vol. 338 https://doi.org/10.1016/j.icarus.2019.113548	journal	March 2020
Sublimation of ices of astrophysical interest: A bibliographic review Fray, N.; Schmitt, B. Planetary and Space Science, Vol. 57, Issue 14-15 https://doi.org/10.1016/j.pss.2009.09.011	journal	December 2009
Modeling survey of ices in Titan's stratosphere Barth, Erika L. Planetary and Space Science, Vol. 137 https://doi.org/10.1016/j.pss.2017.01.003	journal	March 2017
Highly oriented monolayer graphite formation on Pt(111) by a supersonic methane beam Ueta, Hirokazu; Saida, Morihiko; Nakai, Chikara Surface Science, Vol. 560, Issue 1-3 https://doi.org/10.1016/j.susc.2004.04.039	journal	July 2004
A Review of Classical and Nonclassical Nucleation Theories Karthika, S.; Radhakrishnan, T. K.; Kalaichelvi, P. Crystal Growth & Design, Vol. 16, Issue 11 https://doi.org/10.1021/acs.cgd.6b00794	journal	October 2016
Desorption Kinetics of Ar, Kr, Xe, N ₂ , O ₂ , CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces Smith, R. Scott; May, R. Alan; Kay, Bruce D. The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b10033	journal	November 2015
Ordered Structures and Morphology-Induced Phase Transitions at Graphite–Acetonitrile Interfaces Wu, Chengyi; Yang, Ding-Shyue The Journal of Physical Chemistry C, Vol. 123, Issue 36 https://doi.org/10.1021/acs.jpcc.9b06440	journal	August 2019
Structure and Desorption Kinetics of Acetonitrile Thin Films on Pt(111) and on Graphene on Pt(111) Tylinski, M.; Smith, R. Scott; Kay, Bruce D. The Journal of Physical Chemistry C, Vol. 124, Issue 4 https://doi.org/10.1021/acs.jpcc.9b10579	journal	January 2020
No Confinement Needed: Observation of a Metastable Hydrophobic Wetting Two-Layer Ice on Graphene Kimmel, Greg A.; Matthiesen, Jesper; Baer, Marcel Journal of the American Chemical Society, Vol. 131, Issue 35 https://doi.org/10.1021/ja904708f	journal	September 2009
Molecular Dynamics Study of the Liquid−Vapor Interface of Acetonitrile: Equilibrium and Dynamical Properties Paul, Sandip; Chandra, Amalendu The Journal of Physical Chemistry B, Vol. 109, Issue 43 https://doi.org/10.1021/jp055047r	journal	November 2005
Acetonitrile on Silica Surfaces and at Its Liquid−Vapor Interface: Structural Correlations and Collective Dynamics Hu, Zhonghan; Weeks, John D. The Journal of Physical Chemistry C, Vol. 114, Issue 22 https://doi.org/10.1021/jp100350y	journal	May 2010
Interfacial Organization of Acetonitrile: Simulation and Experiment Ding, Feng; Hu, Zhonghan; Zhong, Qin The Journal of Physical Chemistry C, Vol. 114, Issue 41 https://doi.org/10.1021/jp104597z	journal	August 2010
Crystallization Kinetics and Excess Free Energy of H ₂ O and D ₂ O Nanoscale Films of Amorphous Solid Water Smith, R. Scott; Matthiesen, Jesper; Knox, Jake The Journal of Physical Chemistry A, Vol. 115, Issue 23 https://doi.org/10.1021/jp110297q	journal	June 2011
Symmetry and the Surface Infrared Selection Rule for the determination of the Structure of Molecules on Metal Surfaces Fan, Jingfu; Trenary, Michael Langmuir, Vol. 10, Issue 10 https://doi.org/10.1021/la00022a044	journal	October 1994
The organic component in dust from comet Halley as measured by the PUMA mass spectrometer on board Vega 1 Kissel, J.; Krueger, F. R. Nature, Vol. 326, Issue 6115 https://doi.org/10.1038/326755a0	journal	April 1987
Control of amorphous solid water morphology using molecular beams. I. Experimental results Kimmel, Greg A.; Stevenson, K. P.; Dohnálek, Z. The Journal of Chemical Physics, Vol. 114, Issue 12 https://doi.org/10.1063/1.1350580	journal	March 2001
Control of amorphous solid water morphology using molecular beams. II. Ballistic deposition simulations Kimmel, Greg A.; Dohnálek, Z.; Stevenson, K. P. The Journal of Chemical Physics, Vol. 114, Issue 12 https://doi.org/10.1063/1.1350581	journal	March 2001
Intrinsic and extrinsic precursors to adsorption: Coverage and temperature dependence of Kr adsorption on Pt(111) Carlsson, A. F.; Madix, R. J. The Journal of Chemical Physics, Vol. 114, Issue 12 https://doi.org/10.1063/1.1350816	journal	March 2001
Infrared Spectra of Acetonitrile and Acetonitrile‐ d 3 Pace, E. L.; Noe, Lewis J. The Journal of Chemical Physics, Vol. 49, Issue 12 https://doi.org/10.1063/1.1670050	journal	December 1968
Entropy and Related Thermodynamic Properties of Acetonitrile (Methyl Cyanide) Putnam, William E.; McEachern, Douglas Marvin; Kilpatrick, John E. The Journal of Chemical Physics, Vol. 42, Issue 2 https://doi.org/10.1063/1.1696002	journal	January 1965
Infrared Study of Adsorbed Molecules on Metal Surfaces by Reflection Techniques Greenler, Robert G. The Journal of Chemical Physics, Vol. 44, Issue 1 https://doi.org/10.1063/1.1726462	journal	January 1966
The effect of the incident collision energy on the phase and crystallization kinetics of vapor deposited water films Scott Smith, R.; Zubkov, Tykhon; Kay, Bruce D. The Journal of Chemical Physics, Vol. 124, Issue 11 https://doi.org/10.1063/1.2177658	journal	March 2006
Adsorption, desorption, and diffusion of nitrogen in a model nanoporous material. I. Surface limited desorption kinetics in amorphous solid water Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R. The Journal of Chemical Physics, Vol. 127, Issue 18 https://doi.org/10.1063/1.2790432	journal	November 2007
The evaporation rate, free energy, and entropy of amorphous water at 150 K Speedy, Robin J.; Debenedetti, Pablo G.; Smith, R. Scott The Journal of Chemical Physics, Vol. 105, Issue 1 https://doi.org/10.1063/1.471869	journal	July 1996
The release of trapped gases from amorphous solid water films. I. “Top-down” crystallization-induced crack propagation probed using the molecular volcano May, R. Alan; Smith, R. Scott; Kay, Bruce D. The Journal of Chemical Physics, Vol. 138, Issue 10 https://doi.org/10.1063/1.4793311	journal	March 2013
The release of trapped gases from amorphous solid water films. II. “Bottom-up” induced desorption pathways Alan May, R.; Scott Smith, R.; Kay, Bruce D. The Journal of Chemical Physics, Vol. 138, Issue 10 https://doi.org/10.1063/1.4793312	journal	March 2013
Perspective: Highly stable vapor-deposited glasses Ediger, M. D. The Journal of Chemical Physics, Vol. 147, Issue 21 https://doi.org/10.1063/1.5006265	journal	December 2017
Phase transition in solid acetonitrile Torrie, B. H.; Powell, B. M. Molecular Physics, Vol. 75, Issue 3 https://doi.org/10.1080/00268979200100441	journal	February 1992
Detection of Millimeter Emission Lines from Interstellar Methyl Cyanide Solomon, P. M.; Jefferts, K. B.; Penzias, A. A. The Astrophysical Journal, Vol. 168 https://doi.org/10.1086/180794	journal	August 1971
Integration of point-contact microscopy and atomic-force microscopy: Application to characterization of graphite/Pt(111) Enachescu, M.; Schleef, D.; Ogletree, D. F. Physical Review B, Vol. 60, Issue 24 https://doi.org/10.1103/PhysRevB.60.16913	journal	December 1999
CH ₃ CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure Enjalbert, Renée; Galy, Jean Acta Crystallographica Section B Structural Science, Vol. 58, Issue 6 https://doi.org/10.1107/S0108768102017603	journal	November 2002
Deep Impact: Excavating Comet Tempel 1 A'Hearn, M. F. Science, Vol. 310, Issue 5746 https://doi.org/10.1126/science.1118923	journal	October 2005
R EFLECTION A BSORPTION I NFRARED S PECTROSCOPY AND THE S TRUCTURE OF M OLECULAR A DSORBATES ON M ETAL S URFACES Trenary, Michael Annual Review of Physical Chemistry, Vol. 51, Issue 1 https://doi.org/10.1146/annurev.physchem.51.1.381	journal	October 2000

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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