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Electron-withdrawing effects on the molecular structure of 2- and 3-nitrobenzonitrile revealed by broadband rotational spectroscopy and their comparison with 4-nitrobenzonitrile

MPS-Authors
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Graneek,  J. B.
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Deutsches Elektronen-Synchrotron;
CAU Kiel, Institute of Physical Chemistry;

/persons/resource/persons22077

Schnell,  M.
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Deutsches Elektronen-Synchrotron;
CAU Kiel, Institute of Physical Chemistry;

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Fulltext (public)

c8cp01539b.pdf
(Publisher version), 3MB

Supplementary Material (public)

c8cp01539b1.pdf
(Supplementary material), 31MB

Citation

Graneek, J. B., Bailey, W. C., & Schnell, M. (2018). Electron-withdrawing effects on the molecular structure of 2- and 3-nitrobenzonitrile revealed by broadband rotational spectroscopy and their comparison with 4-nitrobenzonitrile. Physical Chemistry Chemical Physics, 34, 22210-22217. doi:10.1039/C8CP01539B.


Cite as: http://hdl.handle.net/21.11116/0000-0001-F647-A
Abstract
The rotational spectra of 2- and 3-nitrobenzonitrile were recorded via chirped-pulse Fourier transform microwave spectroscopy in the frequency range of 2–8 GHz. These molecules each display large dipole moments, making them viable candidates for deceleration and trapping experiments with AC-electric fields. For both molecules, the main isotopologues and all isotopologues of the respective 13C-, 15N-, 18O-monosubstituted species in their natural abundance were assigned. These assignments allowed for the structural determination of 2- and 3-nitrobenzonitrile via Kraitchman's equations as well as a mass-dependent least-squares fitting approach. The experimentally determined structural parameters are then compared to those obtained from quantum-chemical calculations for these two molecules and 4-nitrobenzonitrile. Structural changes caused by steric interaction and competition for the electron density of the phenyl ring highlight how these strong electron-withdrawing substituents affect one another according to their respective positions on the phenyl ring.