Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1250431 | Vibrational Spectroscopy | 2012 | 8 Pages |
Abstract
The vibrational structure of solid 3-fluoroisonicotinic acid, as measured by IR absorption and Raman spectra in the 4000-50 cmâ1 region and aided by B3LYP/6-311++G(d,p) and NBO calculations has been analyzed. While anomalous spectral behavior similar to that in pyridine-carboxylic acids has been observed as two broad medium absorptions 2436 and 1870 cmâ1, the inverted bands observed in isonicotinic acid, are present as 'normal' bands near 1488, 1308, 1132, 1062, and 823 cmâ1. It has been shown by dimer modeling that the absorptions at 2436 and 1308 cmâ1 correspond to OH stretching and in-plane vibrations originating from inter-molecular OHâ¯N bonding. Formation of a network of dimer chains has been shown to be a result of CHâ¯O bond links, giving rise to a local center of inversion between monomer species in the network. This has been validated by observing one broad low intensity Raman band at 1708 cmâ1 and one strong broad IR band at 1727 cmâ1 assigned as symmetric and anti-symmetric carbonyl modes respectively. In the proposed dimer model, the OHâ¯N bond length is calculated to be 2.742 Ã
, shorter than the van der Waals approach, 2.750Â Ã
, placing it in the category of a strong hydrogen bond. The CHâ¯O bond length for the dimer is calculated to be â¼3.282 Ã
. It has been found that the dimer model is only suggestive of the complex nature of OHâ¯N bonding but the results generally are in agreement with experiment.
Keywords
Related Topics
Physical Sciences and Engineering
Chemistry
Analytical Chemistry
Authors
Jayashree Yenagi, Anita Shettar, J. Tonannavar,