The intensity of Rayleigh and Raman scattered light from molecular structural units is proportional to the quadratic polarizability tensor and the derived polarizability tensor, respectively. The orientation of the polymer skeletal backbone is directly related to the orientation of the scattering structural units comprising it. The mathematical structure of the quadratic scattering tensors for a single Kuhn bond are deduced in terms of the unit vector along a Kuhn bond from symmetry considerations alone (Boehler 1987). Subsequent application of the Kuhn–Grün conditional probability analysis (Kuhn and Grün, Kolloid Z 101:248–271, 1942), which uses a freely jointed chain model, yields a general expression for the quadratic Raman and polarizability tensors for a single chain segment with five independent terms. Each term is multiplied by a spectroscopic parameter that is a complex function of the intrinsic spectroscopic tensors and the orientation distribution of monomers within an elementary Kuhn bond. A small stretch analysis of the Kuhn–Grün representation of the quadratic polarizability reveals that independent fourth moments of the segmental orientation distribution function can only be determined experimentally when the deformation or stretch of the flexible polymer is large and finite, thus severely restricting a primary advantage of the Raman and Rayleigh scattering methods. A general segmental additivity theorem is rigorously proven which demonstrates that polarized scattering experiments physically reflect the average orientation and stretch of flexible polymer skeletal backbone segments, or sub-segments, independent of chain architecture or molecular weight. Constitutive equations are fundamentally constructed to determine Kuhn bond orientation and are intrinsically related to the Kuhn–Grün analysis. The decoupling approximation, which is always invoked in Doi–Edwards type models of entangled polymeric liquids, is examined in light of the Kuhn–Grün analysis.

Time-resolved resonance Raman (TR3) spectra have been obtained for Re2X8(2-) (X = Cl, Br) in the 1A2u (sigma-sigma*) electronically excited state, at ambient temperature in solution. The TR3 spectra exhibit Raman peaks that are assigned to the three symmetric vibrations of the excited state: the Re-Re stretch, Re-X stretch, and the Re-Re-X deformation. In addition, a depolarized peak attributed to an asymmetric X-Re-X bend is observed. Comparison of the TR3 results to single-crystal vibronic spectra reported by others clearly shows the effects of crystal constraints and observation time scale upon the structure of the sigma-sigma excited state. The excited-state metal-metal bond distance is inferred to be 0.03-0.04 angstrom shorter in solution than in the crystal. The TR3 data, obtained in solution on the nanosecond time scale, indicate that the excited state relaxes to a staggered molecular structure (D4 or D4d symmetry). The vibronic data, obtained on single crystals under cryogenic conditions, are consistent with an eclipsed (D4h) structure, similar to that of the ground state. A comparative TR3 study of quadruply bonded complexes, including both octahalodirhenate ions and Mo2(PMe3)4Cl4 (which is precluded by steric factors from significant torsional distortion about the metal-metal bond), was essential in elucidating the excited-state structures.

Resonance Raman and Fourier transform infrared spectra of several derivatives of cytochrome ba3, a newly discovered terminal oxidase of the bacterium Thermus thermophilus, are reported. The RR features characteristic of cytochrome a3 are uniquely observed without interference from cytochrome b by subtraction of the analogous cytochrome b5 spectra. The spin state indicator peaks of the a3 heme appear at unusually high frequencies, suggesting a uniquely small heme core size. Multiple C-0 and Fe-N(Im) peaks are observed in the FTIR and RR spectra, respectively. Their relative intensities are temperature-dependent suggesting the presence of discrete interconverting conformers of the enzyme. Thermodynamic parameters for interconversion of these conformers are derived. The C-0 infrared stretching frequencies of the fully reduced carbon-monoxy enzyme show that CO binds to Cue following photodissociation of CO from the heme a3 at all temperatures up to ambient.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMolecular and ionic phases of solid nitrosyl chloride at low temperaturePatrick M. Killough, Basil I. Swanson, and Stephen F. AgnewCite this: J. Phys. Chem. 1989, 93, 23, 7953–7956Publication Date (Print):November 1, 1989Publication History Published online1 May 2002Published inissue 1 November 1989https://pubs.acs.org/doi/10.1021/j100360a041https://doi.org/10.1021/j100360a041research-articleACS PublicationsRequest reuse permissionsArticle Views28Altmetric-Citations5LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts

AbstractResonance enhancement of the NO stretching Raman bands has been observed from dilute solutions (10−3‐10−2 mol dm−3) of some alkyl nitroxyl radicals by excitation into their ultraviolet absorption band (λmax ≈︁ 240 nm). Excitation at 248 nm was produced by a line‐narrowed, pulsed KrF excimer laser. Three overtone bands, which were observed for di‐tert‐butylnitroxyl, showed a small anharmonic contribution, xeνe = 8.8 cm−1.

Using two-colour pump-probe nanosecond pulsed laser techniques we have identified a number of transient species in the photoreactions of anthraquinone-2,6-disulphonate (AQS) and 7-hydroxyflavone (7-FOH) in solution through their resonance Raman (RR) spectra. The anthraquinone system is of interest due to its wide ranging applicability as a photosensitizer [1,2], while the flavone species provides an example of excited state proton-transfer reactions [3].

Conference Article| October 01 1985 Ultraviolet resonance Raman spectroscopy of a highly specific acyl-papain PETER J. TONGE; PETER J. TONGE *Department of Biochemistry, University of Birmingham, P. O. Box 363, Birmingham B15 2TT, U.K. Search for other works by this author on: This Site PubMed Google Scholar CHRISTOPHER W. WHARTON; CHRISTOPHER W. WHARTON *Department of Biochemistry, University of Birmingham, P. O. Box 363, Birmingham B15 2TT, U.K. Search for other works by this author on: This Site PubMed Google Scholar RONALD J. SZAWELSKI; RONALD J. SZAWELSKI *Department of Biochemistry, University of Birmingham, P. O. Box 363, Birmingham B15 2TT, U.K. Search for other works by this author on: This Site PubMed Google Scholar PATRICK M. KILLOUGH; PATRICK M. KILLOUGH †Department of Chemistry, University of York, Heslington, York YO1 1DD, U.K. Search for other works by this author on: This Site PubMed Google Scholar RONALD E. HESTER RONALD E. HESTER †Department of Chemistry, University of York, Heslington, York YO1 1DD, U.K. Search for other works by this author on: This Site PubMed Google Scholar Biochem Soc Trans (1985) 13 (5): 930–931. https://doi.org/10.1042/bst0130930 Views Icon Views Article contents Figures & tables Video Audio Supplementary Data Peer Review Share Icon Share Facebook Twitter LinkedIn MailTo Cite Icon Cite Get Permissions Citation PETER J. TONGE, CHRISTOPHER W. WHARTON, RONALD J. SZAWELSKI, PATRICK M. KILLOUGH, RONALD E. HESTER; Ultraviolet resonance Raman spectroscopy of a highly specific acyl-papain. Biochem Soc Trans 1 October 1985; 13 (5): 930–931. doi: https://doi.org/10.1042/bst0130930 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex toolbar search Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentAll JournalsBiochemical Society Transactions Search Advanced Search This content is only available as a PDF. © 1985 Biochemical Society1985 Article PDF first page preview Close Modal You do not currently have access to this content.

Chemischer InformationsdienstVolume 16, Issue 11 Physical Organic Chemistry ChemInform Abstract: TRIPLET-STATE RESONANCE RAMAN SPECTRUM OF ALL-TRANS-DIPHENYLBUTADIENE R. WILBRANDT, R. WILBRANDTSearch for more papers by this authorW. E. L. GROSSMAN, W. E. L. GROSSMANSearch for more papers by this authorP. M. KILLOUGH, P. M. KILLOUGHSearch for more papers by this authorJ. E. BENNETT, J. E. BENNETTSearch for more papers by this authorR. E. HESTER, R. E. HESTERSearch for more papers by this author R. WILBRANDT, R. WILBRANDTSearch for more papers by this authorW. E. L. GROSSMAN, W. E. L. GROSSMANSearch for more papers by this authorP. M. KILLOUGH, P. M. KILLOUGHSearch for more papers by this authorJ. E. BENNETT, J. E. BENNETTSearch for more papers by this authorR. E. HESTER, R. E. HESTERSearch for more papers by this author First published: March 19, 1985 https://doi.org/10.1002/chin.198511053AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume16, Issue11March 19, 1985 RelatedInformation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTriplet-state resonance Raman spectrum of all-trans-diphenylbutadieneR. Wilbrandt, W. E. L. Grossman, P. M. Killough, J. E. Bennett, and R. E. HesterCite this: J. Phys. Chem. 1984, 88, 24, 5964–5971Publication Date (Print):November 1, 1984Publication History Published online1 May 2002Published inissue 1 November 1984https://pubs.acs.org/doi/10.1021/j150668a044https://doi.org/10.1021/j150668a044research-articleACS PublicationsRequest reuse permissionsArticle Views102Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts

Time-resolved resonance Raman spectra of anthraquinone-2,6-disulphonate (AQ26DS) in oxygenated aqueous solution in the presence of nitrite ion have been obtained. AQ26DS was pumped into the excited singlet state by 337 nm laser excitation and the time evolution of the spectrum observed at a probe laser wavelength of 480 nm. An analysis of the kinetics indicates that the transient spectrum is due to the radical anion of AQ26DS.