DOI: 10.1063/1.1672665. ESR of the CN Radical in Inert Matrices

10.1063/1.1672665

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

CN has been trapped as a randomly oriented molecule in argon, krypton, and neon matrices at 4°K. The ESR spectra of 12C14N and 13C14N in their ground Σ+2 states have been determined and yield the following magnetic parameters in solid argon: g‖ = 2.0015(5), g⊥ = 2.0003(5), A‖(14N) = + 18.2(4) MHz, A⊥ (14N) = − 28.0(3) MHz, A‖ (13C) = + 678(1) MHz, A⊥ (13C) = + 543.1(5) MHz. Weak forbidden ΔMI = ± 1 transitions are also observed. Upon slight warming, the sites are irreversibly changed so that CN thereafter exhibits hindered rotation, even at 4°K, and raising the temperature leads to the isotropic ESR spectrum of rotating CN. Variations in linewidths due to motional effects make it possible to confirm the relative signs of the A values. The g⊥ shift is shown to arise from small negative contributions from spin–orbit coupling with both the Πi2 and Πr2 excited states. Approximate spin densities in the molecule are qC(2s) = 0.19, qC(2p) = 0.48, qN(2p) = 0.32, qN(2s) = − 0.008. These values are compared with those obtained from a Hartree–Fock wavefunction provided by Cade.

Bibliography

Easley, W. C., & Weltner, W. (1970). ESR of the CN Radical in Inert Matrices. The Journal of Chemical Physics, 52(1), 197â205.

Authors 2

Warren C. Easley (first)
William Weltner (additional)

References 30 Referenced 107

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Dates

Type	When
Created	21 years, 7 months ago (Feb. 6, 2004, 2:23 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 1:11 a.m.)
Indexed	4 days, 6 hours ago (Sept. 3, 2025, 5:53 a.m.)
Issued	55 years, 8 months ago (Jan. 1, 1970)
Published	55 years, 8 months ago (Jan. 1, 1970)
Published Print	55 years, 8 months ago (Jan. 1, 1970)

Funders 0

None

BibTeX

@article{Easley_1970, title={ESR of the CN Radical in Inert Matrices}, volume={52}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1672665}, DOI={10.1063/1.1672665}, number={1}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Easley, Warren C. and Weltner, William}, year={1970}, month=jan, pages={197–205} }

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  "abstract": "<jats:p>CN has been trapped as a randomly oriented molecule in argon, krypton, and neon matrices at 4\u00b0K. The ESR spectra of 12C14N and 13C14N in their ground \u03a3+2 states have been determined and yield the following magnetic parameters in solid argon: g\u2016\u2009=\u20092.0015(5), g\u22a5\u2009=\u20092.0003(5), A\u2016(14N)\u2009=\u2009+\u200918.2(4) MHz, A\u22a5 (14N)\u2009=\u2009\u2212\u200928.0(3) MHz, A\u2016 (13C)\u2009=\u2009+\u2009678(1) MHz, A\u22a5 (13C)\u2009=\u2009+\u2009543.1(5) MHz. Weak forbidden \u0394MI\u2009=\u2009\u00b1\u20091 transitions are also observed. Upon slight warming, the sites are irreversibly changed so that CN thereafter exhibits hindered rotation, even at 4\u00b0K, and raising the temperature leads to the isotropic ESR spectrum of rotating CN. Variations in linewidths due to motional effects make it possible to confirm the relative signs of the A values. The g\u22a5 shift is shown to arise from small negative contributions from spin\u2013orbit coupling with both the \u03a0i2 and \u03a0r2 excited states. Approximate spin densities in the molecule are qC(2s)\u2009=\u20090.19, qC(2p)\u2009=\u20090.48, qN(2p)\u2009=\u20090.32, qN(2s)\u2009=\u2009\u2212\u20090.008. These values are compared with those obtained from a Hartree\u2013Fock wavefunction provided by Cade.</jats:p>",
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