{"title":"CH-Bindungsmomente und IR-Intensitäten von Benzol-Derivaten—V. Theorie","authors":"E.D. Schmid","doi":"10.1016/0371-1951(66)80166-2","DOIUrl":"10.1016/0371-1951(66)80166-2","url":null,"abstract":"<div><p>It is shown that a complete parametrisation of the intensities of the CH-stretching vibrations of benzene and its derivatives is possible. The intensity I<sub>CH</sub> for such a compound can be expressed by a relation <em>I</em><sub>CH</sub>=<figure><img></figure>(frcase|∂μ/∂<em>R<sub>j</sub></em>)<sup>2</sup>=<em>F</em>(<em>a<sub>j</sub></em>, σ<em><sub>I</sub></em>) which can be explicitly stated. σ<em><sub>I</sub></em> is the T<span>aft</span> substituent constant and the <em>a<sub>j</sub></em> can be empirically determined. From the above relation there was obtained a function for the derivative of the dipole moment of the <em>j</em>-th CH bond with respect to the <em>j</em>-th stretching coordinate: <span><math><mtext>∂μ</mtext><msub><mi></mi><mn>j</mn></msub><mtext>∂</mtext><mtext>R</mtext><msub><mi></mi><mn>j</mn></msub></math></span> = <em>F</em>(<em>a<sub>j</sub></em>, σ<em><sub>I</sub></em>) Under reasonable assumptions this function can be integrated, thus leading to a functional relation between the CH dipole moment μ<em><sub>j</sub></em> and the substituent σ<em><sub>I</sub></em>. The results show that for benzene and most benzene derivatives the polarity of the CH bond is C<sup>+</sup>H<sup>−</sup>. In fact, all substituents having σ<em><sub>I</sub></em>— values greater than zero induce a C<sup>−</sup>H<sup>+</sup> polarity. There are, however, some <em>para</em> disubstituted benzene derivatives where the dipole moments induced by the substituents are so great as to lead to a C<sup>−</sup>H<sup>+</sup> polarity of the CH-bond.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 9","pages":"Pages 1659-1675"},"PeriodicalIF":0.0,"publicationDate":"1966-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80166-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83965842","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Vibrational spectra of hexahalocyclopropanes and tetrahalocyclopropenes","authors":"M. Ito","doi":"10.1016/0371-1951(66)80158-3","DOIUrl":"10.1016/0371-1951(66)80158-3","url":null,"abstract":"<div><p>Raman and infra-red spectra are reported for hexachlorocyclopropane (I), hexa-bromocyclopropane (II), hexafluorocyclopropane (III), tetrachlorocyclopropene (IV) and tetra-bromocyclopropene (V). A vibrational assignment is made for I, II and III on the basis of <em>D</em><sub>3</sub><em><sub>h</sub></em> symmetry and for IV and V on the basis Of <em>C</em><sub>2</sub><em><sub>v</sub></em> symmetry.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 9","pages":"Pages 1581-1589"},"PeriodicalIF":0.0,"publicationDate":"1966-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80158-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72596442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"CH-Bindungsmomente und IR-Intensität von Benzol-Derivaten—II. CH- und CD-Valenzschwingungen deuterierter Benzol-Monoderivate","authors":"E.D. Schmid, F. Langenbucher","doi":"10.1016/0371-1951(66)80163-7","DOIUrl":"10.1016/0371-1951(66)80163-7","url":null,"abstract":"<div><p>The absorption intensities of the CH and CD stretching vibrations of some deuterated benzene monoderivatives have been measured in CCl<sub>4</sub> solution. The compounds are of the type 4-D-phenyl-X and 2,4,6-D<sub>3</sub>-phenyl-X. The observed intensities can be interpreted as sum of contributions <em>I<sub>o</sub></em>, <em>I<sub>m</sub></em>, and <em>I<sub>p</sub></em>, of the participating CH or CD oscillators. By using also the data for the undeuterated compounds phenyl-X these bond contributions can be evaluated separately. They show a decrease with the T<span>aft</span> substituent parameter σ<sub>I</sub>, that is greatest in <em>ortho</em> and smallest in <em>para</em> position. The isotope intensity sum rule is verified for the CH and CD stretching vibrations in all the cases considered.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 9","pages":"Pages 1621-1632"},"PeriodicalIF":0.0,"publicationDate":"1966-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80163-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72909368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Infrared intensity measurements—III. Correlation functions of chloroethylenes","authors":"J.T Shimozawa , M.K Wilson","doi":"10.1016/0371-1951(66)80161-3","DOIUrl":"10.1016/0371-1951(66)80161-3","url":null,"abstract":"<div><p>The analysis of infrared band shapes through correlation functions as developed by G<span>ordon</span> and S<span>himizu</span> has been applied to the chloroethylenes. Reasonable agreement with S<span>himizu's</span> theory has been achieved and the results compared with those of G<span>ordon</span>.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 9","pages":"Pages 1609-1614"},"PeriodicalIF":0.0,"publicationDate":"1966-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80161-3","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83819222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"CH-Bindungsmomente und IR-Intensität von Benzol-Derivaten—III. CH-Valenzschwingungen para-disubstituierter Benzol-Derivate","authors":"E.D. Schmid, V. Hoffmann","doi":"10.1016/0371-1951(66)80164-9","DOIUrl":"10.1016/0371-1951(66)80164-9","url":null,"abstract":"<div><p>To analyse the interaction between substituents and aromatic CH bonds the intensities of the CH<sub>ar</sub> stretching vibrations of 32 <em>para</em>-disubstituted benzene derivatives have been measured. For three discernible groups of <em>p</em>-benzene derivatives resulted a correlation between intensities and the sum of inductive parameters of Hammett constants [σ<em><sub>I</sub></em>(<em>X</em>) + σ<em><sub>I</sub></em>(<em>Y</em>)]. It was possible to invert the polarity of the moments of the CH bonds by strong electron acceptors. Hence the assumption of a C<sup>+</sup>H<sup>−</sup> polarity in undisturbed benzene could be confirmed.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 9","pages":"Pages 1633-1643"},"PeriodicalIF":0.0,"publicationDate":"1966-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80164-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86687584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Spectra structure correlations in hydroxy and fluorapatite","authors":"C.B. Baddiel, E.E. Berry","doi":"10.1016/0371-1951(66)80133-9","DOIUrl":"10.1016/0371-1951(66)80133-9","url":null,"abstract":"<div><p>The infra-red spectra of synthetic hydroxyapatite, Ca<sub>10</sub>(PO<sub>4</sub>)<sub>6</sub>(OH)<sub>2</sub>, and mineral fluorapatite, Ca<sub>10</sub>(PO<sub>4</sub>)<sub>6</sub>F<sub>2</sub>, over the range 4000-250 cm<sup>−1</sup> are reported. Comparison with the “free” phosphate ion indicates considerable perturbation of the PO<sub>4</sub><sup>3−</sup> group in these solids; the observed absorptions suggest that in both compounds the phosphate symmetry is lowered to the extent predicted by a site symmetry analysis i.e. to <em>C</em><sub>1</sub> in hydroxyapatite and <em>C<sub>s</sub></em> in fluorapatite, but the splitting of degenerate modes is not complete; this effect is more noticeable in fluorapatite. A weak interatomic crystal field arising out of the relatively low density of the atomic packing in these compounds is suggested as a cause of this incomplete removal of degeneracies. The spectroscopic evidence for the existence of hydrogen bonding of the OH … OPO<sub>3</sub> type in hydroxyapatite is discussed.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 8","pages":"Pages 1407-1416"},"PeriodicalIF":0.0,"publicationDate":"1966-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80133-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76989390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Absolute infrared intensities in crystalline acetylene and ethane","authors":"D.A. Dows","doi":"10.1016/0371-1951(66)80141-8","DOIUrl":"10.1016/0371-1951(66)80141-8","url":null,"abstract":"<div><p>Absolute infrared absorption intensities have been measured for three bands of crystalline acetylene and two bands (the hydrogen stretching motions) of crystalline ethane. The changes of intensity observed on condensation of the gases cannot be explained as a “dielectric effect”. In acetylene the large frequency shift and intensification of the hydrogen stretching mode are consistent with characterization of the intermolecular forces as hydrogen bonding to the acetylenic π-clouds.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 8","pages":"Pages 1479-1481"},"PeriodicalIF":0.0,"publicationDate":"1966-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80141-8","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79911534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Infrared absorption spectra of metal-amino acid complexes—V. The infrared spectra and normal vibrations of metal-leucine chelates","authors":"J.F. Jackovitz, J.L. Walter C.S.C.","doi":"10.1016/0371-1951(66)80132-7","DOIUrl":"https://doi.org/10.1016/0371-1951(66)80132-7","url":null,"abstract":"<div><p>The infrared spectra of <span>dl</span>-leucine and some metal-leucine complexes have been investigated from 3600 to 33 cm<sup>−1</sup>. A detailed normal coordinate analysis was performed for the metal complexes and an approximate description of the vibrational mode has been assigned to most of the observed frequencies. Calculated values of the metal-nitrogen bond-stretching force constants vary in the order Pt(II) > Pd(II) > Cu(II) > Zn(II) > Cd(II) > Ni(II) ∼ Co(II) which indicates a corresponding variation in the strength of the metal-nitrogen bond.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 8","pages":"Pages 1393-1406"},"PeriodicalIF":0.0,"publicationDate":"1966-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80132-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136603129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Vibrational spectra of para-fluoro- and para-chloroanisole","authors":"J.N. Rai, K.N. Upadhya","doi":"10.1016/0371-1951(66)80135-2","DOIUrl":"10.1016/0371-1951(66)80135-2","url":null,"abstract":"<div><p>The infra-red absorption spectra of liquid <em>p</em>-fluoro- and <em>p</em>-chloroanisole have been recorded. Vibrational assignments have been made on the basis of <em>C<sub>s</sub></em> symmetry.</p></div>","PeriodicalId":101180,"journal":{"name":"Spectrochimica Acta","volume":"22 8","pages":"Pages 1427-1430"},"PeriodicalIF":0.0,"publicationDate":"1966-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0371-1951(66)80135-2","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74919656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}