The effect of pressure on the Raman spectra of solids. VII. The internal Raman bands in solid and coordinated pyridine

Article abstract of DOI:10.1063/1.459389

The pressure dependences of the internal Raman-active modes of solid pyridine and pyridine-d₅ in both the crystalline and glassy modifications as well as of the complexes Zn(py)2Cl2, Ni(py)2Cl2, and Ni(py)4Cl2 are reported.When pyridine is frozen by the application of pressure, some ring modes as well as those involving the hydrogen atoms reflect this transformation.Upon the coordination of pyridine to metal ions, the ring vibrations show appreciable blue shifts.The pressure dependences of ν₁, the C-C stretching mode, and ν₁₂, the in-plane ring bending mode of the pyridine rings, are discussed in detail.The unusually high d₅-h₅ isotopic ratio of ν₁₂ and its contrasting pressure dependences in the liquid and condensed phases of pyridine-d₅ are explained.The association of pyridine molecules in the condensed phase does not occur through hydrogen bonds and the C-H stretching modes, in particular, show that repulsive intermolecular forces become very significant at higher pressures.The ratio of the intensities Ιν₁₂/Ιν₁ varies linearly with the strength of the M-N bonds in a series of pyridine complexes and a correlation also exists between Ιν₁₂/Ιν₁ and δν₁₂/δp.The vibrations ν₁ and ν₂ are coupled through Fermi resonance in pyridine and its complexes and the pressure dependence of the Fermi resonance constant W is calculated for Zn(py)2Cl2.The C-H stretching modes reflect the presence of more than one distinct pyridine group in the lattice and are of much lower intensity than in complexes where only one distinct pyridine group is found.

Full text of DOI:10.1063/1.459389

The effect of pressure on the Raman spectra of solids. VII. The internal Raman bands
in solid and coordinated pyridine
A. M. Heyns and M. W. Venter
Citation: The Journal of Chemical Physics 93, 7581 (1990); doi: 10.1063/1.459389
View online: http://dx.doi.org/10.1063/1.459389
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/93/11?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
157.182.150.22 On: Wed, 19 Nov 2014 15:54:27