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Title: Structural and spectroscopic studies of nitrogen-carbon monoxide mixtures: Photochemical response and observation of a novel phase

Authors:
ORCiD logo [1];  [2];  [1]; ORCiD logo [2]
  1. U.S. Army Research Laboratory, RDRL-WML-B, Aberdeen Proving Grounds, Aberdeen, Maryland 21005, USA
  2. Department of Physics, University of South Florida, Tampa, Florida 33620, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1361871
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 18; Related Information: CHORUS Timestamp: 2018-02-14 09:55:11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Ciezak-Jenkins, Jennifer A., Steele, Brad A., Borstad, Gustav M., and Oleynik, Ivan I. Structural and spectroscopic studies of nitrogen-carbon monoxide mixtures: Photochemical response and observation of a novel phase. United States: N. p., 2017. Web. doi:10.1063/1.4983040.
Ciezak-Jenkins, Jennifer A., Steele, Brad A., Borstad, Gustav M., & Oleynik, Ivan I. Structural and spectroscopic studies of nitrogen-carbon monoxide mixtures: Photochemical response and observation of a novel phase. United States. doi:10.1063/1.4983040.
Ciezak-Jenkins, Jennifer A., Steele, Brad A., Borstad, Gustav M., and Oleynik, Ivan I. Sun . "Structural and spectroscopic studies of nitrogen-carbon monoxide mixtures: Photochemical response and observation of a novel phase". United States. doi:10.1063/1.4983040.
@article{osti_1361871,
title = {Structural and spectroscopic studies of nitrogen-carbon monoxide mixtures: Photochemical response and observation of a novel phase},
author = {Ciezak-Jenkins, Jennifer A. and Steele, Brad A. and Borstad, Gustav M. and Oleynik, Ivan I.},
abstractNote = {},
doi = {10.1063/1.4983040},
journal = {Journal of Chemical Physics},
number = 18,
volume = 146,
place = {United States},
year = {Sun May 14 00:00:00 EDT 2017},
month = {Sun May 14 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4983040

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • Vibrational spectra of liquid nitrogen/carbon monoxide mixtures, shock compressed to several high-pressure/high-temperature states, were obtained using single-pulse multiplex coherent anti-Stokes Raman scattering (CARS). The experimental spectra were compared to synthetic spectra calculated with a semiclassical model for CARS intensities and using best fit vibrational frequencies, peak Raman susceptibilities, and Raman linewidths. Up to a maximum shock pressure of 9.3 GPa, both the N[sub 2] and CO vibrational frequencies were found to increase monotonically with pressure but depended strongly on the nitrogen/carbon monoxide mixture ratio. An empirical fit of the Raman frequency shifts incorporating previously published neat nitrogen and carbon monoxidemore » data, using a functional form dependent on pressure, temperature, and mixture ratio, accurately describes both the N[sub 2] and CO shifts. The transition intensity and linewidth data suggest that thermal equilibrium of the vibrational levels is attained in less than 10 ns at these shock pressures and the vibrational temperatures obtained were used to improve the potential function used to calculate equation-of-state pressures and temperatures. The measured linewidths were different for N[sub 2] and CO and suggest that the vibrational dephasing time decreased to a few ps at the highest pressure shock state.« less
  • A two-stage light gas gun and single-pulse multiplex coherent anti-Stokes Raman scattering (CARS) have been used to obtain carbon monoxide, nitrogen, and oxygen vibrational spectra for several high-pressure/high-temperature, dense fluid, mixtures. The experimental spectra were compared to synthetic spectra calculated with a semiclassical model for CARS intensities and using best fit vibrational frequencies, peak Raman susceptibilities, and Raman linewidths for each mixture component. Up to a maximum shock pressure of 6.75 GPa for carbon monoxide{endash}oxygen mixtures, the CO and O{sub 2} vibrational frequencies were found to increase monotonically with pressure and depended on the carbon monoxide{endash}oxygen mixture ratio. For themore » nitrogen{endash}oxygen mixtures, the N{sub 2} vibrational frequency increased monotonically with pressure to a maximum experimental pressure of 12.9 GPa, however the O{sub 2} vibrational frequency increased with pressure to about 11 GPa and then appeared to decrease slightly as the pressure increased to the experiment maximum of 12.9 GPa. Empirical fits of the measured Raman frequencies incorporating previously published neat nitrogen, carbon monoxide, and oxygen data and using a functional form dependent on pressure, temperature, and mixture ratio, accurately describe the N{sub 2}, CO, and O{sub 2} vibrational frequency shifts for both the carbon monoxide{endash}oxygen and the nitrogen{endash}oxygen mixtures. The transition intensity and linewidth data suggest that thermal equilibrium of the vibrational levels is attained in less than 10 ns at these shock pressures. The vibrational temperatures obtained for the nitrogen{endash}oxygen mixtures were used to improve the oxygen potential function used to calculate equation-of-state pressures and temperatures. The measured linewidths for CO, N{sub 2}, and O{sub 2} were different for the different mixtures and did not appear to depended significantly on mixture ratios. (Abstract Truncated)« less
  • This paper reports the synthesis and characterization of chlorobis(pentamethylcyclopentadienyl)thorium and -uranium dialkylamides, M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(NR/sub 2/)Cl (M = Th, U; R = CH/sub 3/, C/sub 2/H/sub 5/), and bis(dialkylamides), M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(NR/sub 2/)/sub 2/ (M = Th, U, R = CH/sub 3/; M = U, R = C/sub 2/H/sub 5/). The amide compounds undergo facile migratory insertion of carbon monoxide to produce the corresponding eta/sup 2/-carbamoyl complexes M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)Cl, M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)NR/sub 2/, and M(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CONR/sub 2/)/sub 2/ which were characterized by amore » variety of chemical and physicochemical methods. The infrared spectra of these compounds exhibit unusually low C-O stretching frequencies (1490 to 1560 cm/sup -1/) for carbamoyl complexes, indicative of strong metal-oxygen bonding. The molecular structures of Th(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sup 2/-CON(C/sub 2/H/sub 5/)/sub 2/)Cl and U(eta-(CH/sub 3/)/sub 5/C/sub 5/)/sub 2/(eta/sub 2/-CON(CH/sub 3/)/sub 2/)/sub 2/ have been determined by single-crystal x-ray diffraction techniques. For the chloro complex, least-squares refinement led to a value for the conventional R index (on F) of 0.080 for 3156 independent reflections having 2theta/sub MoK..cap alpha../ < 55/sup 0/ and I > 3sigma(I), while for the bis(carbamoyl), least-squares refinement led to a conventional R (on F) of 0.036 for 3689 independent reflections having 2 theta/sub MoK..cap alpha../ < 55/sup 0/ and I > 3sigma(I). The M((CH/sub 3/)/sub 5/C/sub 5/)/sub 2/ fragments of both molecules are of the bent sandwich M(C/sub 5/H/sub 5/)/sub 2/X/sub 2/ configuration, with the carbamoyl ligands bound in a eta/sup 2/ fashion. In the bis(carbamoyl), the U-O distances are 2.370 (5) and 2.342 (7) A, the corresponding U-C distances 2.405 (8) and 2.402 (9) A, and the corresponding U-C-O angles 73.0 (4) and 71.8 (5)/sup 0/. The structural and spectral data evidence dative nitrogen lone-pair donation to the carbenoid carbamoyl carbon atom. 6 figures, 8 tables.« less