Rotational spectra, nuclear quadrupole hyperfine tensors, and conformational structures of the mustard gas simulent 2-chloroethyl ethyl sulfide

Tubergen, Michael J.; Lesarri, Alberto; Suenram, R. D.; Samuels, Alan C.; Jensen, James O.; Ellzy, Michael W.; Lochner, J. M.

doi:10.1016/j.jms.2005.06.014

Cited by 6 publications

(3 citation statements)

References 12 publications

(23 reference statements)

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“…3 The structures of the individual conformations can be identified from the spectra by comparing the experimental moments of inertia to moments of inertia calculated from model structures determined by ab initio methods. Additional information used in conformational assignments include isotopically labeled species, nuclear quadrupole hyperfine coupling constants, and dipole moments; conformational assignments using these methods have been made for chloroethyl ethyl sulfide, 11 2-pentanol and 2-hexanol, 12 and methamphetamine and its related precursors 13 among others.…”

Section: Introductionmentioning

confidence: 99%

Rotational spectra of o-, m-, and p-cyanophenol and internal rotation of p-cyanophenol

Conrad

Barefoot

Tubergen

2010

Phys. Chem. Chem. Phys.

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Rotational spectra of p-, m-, and o-cyanophenol have been measured in the range of 10.5-21 GHz and fit using Watson's A-reduction Hamiltonian coupled with nuclear quadrupole coupling interaction terms for the (14)N nuclei. Ab initio calculations at the MP2/6-311++G(d,p) and CCSD(T)/6-311++G(d,p) levels predict the cis conformers of m- and o-cyanophenol to be more stable than the corresponding trans conformers. A natural bond orbital analysis of the hydrogen bonding interaction in o- and m-cyanophenol revealed an intramolecular hydrogen bond that preferentially stabilizes the cis conformer of o-cyanophenol but there was no evidence of hydrogen bonding interactions in cis m-cyanophenol. We recorded 25 a- and b-type rotational transitions for cis o-cyanophenol; the rotational constants are A = 3053.758(2) MHz, B = 1511.2760(3) MHz, and C = 1010.7989(2) MHz. The trans conformer of o-cyanophenol was not observed. We recorded 14 a- and b-type rotational transitions for cis m-cyanophenol and 16 a- and b-type rotational transitions for trans m-cyanophenol. The rotational constants are A = 3408.9200(2) MHz, B = 1205.8269(2) MHz, and C = 890.6672(1) MHz and A = 3403.1196(3) MHz, B = 1208.4903(2) MHz, and C = 891.7241(2) MHz for the cis and trans species, respectively. Rotational transitions of the p-cyanophenol monomer are split due to the internal rotation of the hydroxyl group with respect to the aromatic ring. We recorded 25 a- and b-type rotational transitions for p-cyanophenol; the b-type transitions are split by 40 MHz. The rotational constants are A = 5612.96(2) MHz, B = 990.4283(6) MHz, and C = 841.9363(6) MHz. The ground state spitting DeltaE is 20.1608(6) MHz and the barrier to internal rotation, V(2), is 1413(2) cm(-1) from a fit of the rotational transitions to an internal axis system Hamiltonian. The barrier to internal rotation was modeled at the MP2/6-311++G(d,p) level and the effects of substituents on the phenolic ring and the barriers to internal rotation are discussed.

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Section: Introductionmentioning

confidence: 99%

Rotational spectra of o-, m-, and p-cyanophenol and internal rotation of p-cyanophenol

Conrad

Barefoot

Tubergen

2010

Phys. Chem. Chem. Phys.

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“…The rotational constant and projections of the permanent dipole moment on the inertial axes have been reported previously and are reproduced in Table 1. 28 …”

Section: Pure Rotational Spectramentioning

confidence: 99%

Chirped-Pulse Fourier Transform Microwave Spectroscopy: A New Technique for Rapid Identification of Chemical Agents

Pajski

LOGAN

Douglass

et al. 2008

Int. J. Hi. Spe. Ele. Syst.

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We have developed a new broadband Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectrometer that allows the microwave spectrum in the 7.5-18.5 GHz range to be measured in a single data event. This technique produces a pure rotational spectrum that can be used for unambiguous identification of any species having a permanent electric dipole moment. CP-FTMW is a gas phase technique that is ideally suited for the detection of airborne chemical warfare agents (CWA) which must be detected in trace amounts (< 10 ppm in air). The high resolution of the technique allows the identification of complex mixtures without the need for a preliminary separation step, such as gas chromatography, which significantly reduces analysis time. The technique is "blind" to major atmospheric components (N 2 , O 2 , CO 2 , H 2 O) as they either do not posses a permanent dipole moment or do not absorb in the range of the spectrometer, thereby eliminating large background signals. In this paper we will present preliminary results that are focused on early detection of airborne CWA, including acquisition time, sensitivity limits, and sample handling requirements for several of these species.

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“…The conformational structures present in the expansion can then be identified by comparing the spectroscopically determined moments of inertia to moments of inertia calculated from theoretical model structures; sometimes data from isotopically substituted species, dipole moments, and nuclear quadrupole hyperfine constants are used to support the conformer assignments. Conformational assignments have been made in this way for chloroethyl ethyl sulfide (CEES; a mustard gas simulent) [2], methamphetamine and its related precursors [3], the long-chain aldehyde 1-heptanal [4], as well as the series of long-chain alkenes 1-pentene through 1-dodecene [5][6][7][8][9]. The number of possible conformers increases very rapidly (ca.…”

Section: Introductionmentioning

confidence: 99%

Gas-phase conformational distributions for the 2-alkylalcohols 2-pentanol and 2-hexanol from microwave spectroscopy

Tubergen

Conrad

Chavez

et al. 2008

Journal of Molecular Spectroscopy

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Rotational spectra, nuclear quadrupole hyperfine tensors, and conformational structures of the mustard gas simulent 2-chloroethyl ethyl sulfide

Cited by 6 publications

References 12 publications

Rotational spectra of o-, m-, and p-cyanophenol and internal rotation of p-cyanophenol

Rotational spectra of o-, m-, and p-cyanophenol and internal rotation of p-cyanophenol

Chirped-Pulse Fourier Transform Microwave Spectroscopy: A New Technique for Rapid Identification of Chemical Agents

Gas-phase conformational distributions for the 2-alkylalcohols 2-pentanol and 2-hexanol from microwave spectroscopy

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