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Title: High-resolution infrared studies of the v 10, v 11, v 14, and v 18 levels of [1.1.1]propellane

Abstract

This paper is a continuation of earlier work for which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands v 10 (E'-A1'), v 11 (E'-A1'), v 14 (A2''-A1') and two difference bands (v 10- v 18) (E'-E'') and (v 11-v 18) (E'-E"). Additional information about v18 was also obtained from the difference band (v 15+v 18)-v 18 (E'-E") and the binary combination band (v 15+v 18) (E'-A1'). Through the use of the ground state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the v 18(E'') state were obtained from combination-differences and showed no need to include interactions with other states. The v 10(E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the v 14(A2'') state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby v 11(E') state and also by a small but significant interaction with another state, presumably themore » v16(E'') state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the v 11 and v 14 states and, using a weak coupling term corresponding to a Δk = ±5, Δl = ∓1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C 0 = 0.1936519(4) cm -1. This result, combined with the value of B 0 = 0.28755833(14) cm-1 reported earlier [1], yields a value of 1.586282(3) Å for the length of the novel axial CC bond in propellane.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [4];  [5]
  1. Oregon State Univ., Corvallis, OR (United States)
  2. California State Univ., Hayward, CA (United States)
  3. 14012 24th Ave., Mill Creek, WA (United States)
  4. National Inst. of Standards and Technology, Gaithersburg, MD (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1059615
Report Number(s):
PNNL-SA-89494
Journal ID: ISSN 0022-2852; 20907; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Molecular Spectroscopy
Additional Journal Information:
Journal Volume: 281; Journal ID: ISSN 0022-2852
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Environmental Molecular Sciences Laboratory

Citation Formats

Kirkpatrick, Robynne W., Masiello, Tony, Martin, Matthew A., Nibler, Joseph W., Maki, Arthur, Weber, Alfons, and Blake, Thomas A. High-resolution infrared studies of the v10, v11, v14, and v18 levels of [1.1.1]propellane. United States: N. p., 2012. Web. doi:10.1016/j.jms.2012.09.001.
Kirkpatrick, Robynne W., Masiello, Tony, Martin, Matthew A., Nibler, Joseph W., Maki, Arthur, Weber, Alfons, & Blake, Thomas A. High-resolution infrared studies of the v10, v11, v14, and v18 levels of [1.1.1]propellane. United States. doi:10.1016/j.jms.2012.09.001.
Kirkpatrick, Robynne W., Masiello, Tony, Martin, Matthew A., Nibler, Joseph W., Maki, Arthur, Weber, Alfons, and Blake, Thomas A. Thu . "High-resolution infrared studies of the v10, v11, v14, and v18 levels of [1.1.1]propellane". United States. doi:10.1016/j.jms.2012.09.001.
@article{osti_1059615,
title = {High-resolution infrared studies of the v10, v11, v14, and v18 levels of [1.1.1]propellane},
author = {Kirkpatrick, Robynne W. and Masiello, Tony and Martin, Matthew A. and Nibler, Joseph W. and Maki, Arthur and Weber, Alfons and Blake, Thomas A.},
abstractNote = {This paper is a continuation of earlier work for which the high resolution infrared spectrum of [1.1.1]propellane was measured and its k and l structure resolved for the first time. Here we present results from an analysis of more than 16,000 transitions involving three fundamental bands v10 (E'-A1'), v11 (E'-A1'), v14 (A2''-A1') and two difference bands (v10- v18) (E'-E'') and (v11-v18) (E'-E"). Additional information about v18 was also obtained from the difference band (v15+v18)-v18 (E'-E") and the binary combination band (v15+v18) (E'-A1'). Through the use of the ground state constants reported in an earlier paper [1], rovibrational constants have been determined for all the vibrational states involved in these bands. The rovibrational parameters for the v18(E'') state were obtained from combination-differences and showed no need to include interactions with other states. The v10(E') state analysis was also straight-forward, with only a weak Coriolis interaction with the levels of the v14(A2'') state. The latter levels are much more affected by a strong Coriolis interaction with the levels of the nearby v11(E') state and also by a small but significant interaction with another state, presumably the v16(E'') state, that is not directly observed. Gaussian calculations (B3LYP/cc-pVTZ) computed at the anharmonic level aided the analyses by providing initial values for many of the parameters. These theoretical results generally compare favorably with the final parameter values deduced from the spectral analyses. Finally, evidence was obtained for several level crossings between the rotational levels of the v11 and v14 states and, using a weak coupling term corresponding to a Δk = ±5, Δl = ∓1 matrix element, it was possible to find transitions from the ground state that, combined with transitions to the same upper state, give a value of C0 = 0.1936519(4) cm-1. This result, combined with the value of B0 = 0.28755833(14) cm-1 reported earlier [1], yields a value of 1.586282(3) Å for the length of the novel axial CC bond in propellane.},
doi = {10.1016/j.jms.2012.09.001},
journal = {Journal of Molecular Spectroscopy},
issn = {0022-2852},
number = ,
volume = 281,
place = {United States},
year = {2012},
month = {11}
}