Infrared circular dichroism of carbon-hydrogen and carbon-deuterium stretching modes. Observations

Holzwarth, G.; Hsu, Edward C.; Mosher, Harry S.; Faulkner, Thomas; Moscowitz, Albert

doi:10.1021/ja00808a042

Cited by 285 publications

(125 citation statements)

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“…2 If one considers a single normal mode Q p , i.e. if one assumes a single component p only of Q to be different from zero, then the mass-weighted displacement vector q α,p of nucleus α is given by…”

Section: Representation Of Nuclear Displacement Vectorsmentioning

confidence: 99%

“…One way is through the calculation of vibrational absorption intensities, and of Raman scattering intensities and depolarization ratios, but for non-symmetric molecules nuclear motions are not uniquely related to these quantities [1]. For chiral molecules, two powerful tools for judging the correct rendering of vibrational nuclear motions are vibrational circular dichroism (VCD) [2][3][4] and Raman optical activity (ROA) [5][6][7]. Even with these methods, experimental confirmation of computed nuclear motions requires the agreement not just of individual bands but of patterns of bands, and of changes in patterns with changes in molecular structure, in observed and computed vibrational spectra.…”

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confidence: 99%

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Characterizing vibrational motion beyond internal coordinates

Hug

Fedorovsky

2006

Theor Chem Account

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We present a procedure for the decomposition of the normal modes of a composite system, including its rotations and translations, into those of fragments. The method permits-by the cross-contraction of dyads of mass-weighted displacement vectors, without recourse to valence coordinates-the direct comparison of nuclear motions of structurally similar but otherwise arbitrary fragments of molecules, and it leads to a quantitative definition of the similarity and the overlap of nuclear motions. We illustrate its usefulness by the quantification of the mixing of the normal modes of formic acid monomers upon the formation of a dimer, by the comparison of the overlap of the intermolecular normal vibrations of the water dimer computed with different ab initio schemes, and by the comparison of similarity and overlap of vibrations of (4S,7R)-galaxolide and (4S)-4-methylisochromane. The approach is expected to become a standard tool in vibrational analysis.

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Section: Representation Of Nuclear Displacement Vectorsmentioning

confidence: 99%

mentioning

confidence: 99%

Characterizing vibrational motion beyond internal coordinates

Hug

Fedorovsky

2006

Theor Chem Account

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“…This work is now recognized as the first observation of VOA of molecular origin [80]. This was followed in 1974 by the first report using the more obvious approach using circular dichroism of infrared radiation (VCD) by George Holzwarth and colleagues working at the University of Chicago [56]. These first attempts to measure ROA were highly controversial, with several groups publishing the large polarization artefacts to which such measurements are highly susceptible, and claiming them as real ROA.…”

Section: History Of Roamentioning

confidence: 99%

The development of biomolecular Raman optical activity spectroscopy

Barron

2015

BSI

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Abstract. Following its first observation over 40 years ago, Raman optical activity (ROA), which may be measured as a small difference in the intensity of vibrational Raman scattering from chiral molecules in right-and left-circularly polarized incident light or, equivalently, the intensity of a small circularly polarized component in the scattered light using incident light of fixed polarization, has evolved into a powerful chiroptical spectroscopy for studying a large range of biomolecules in aqueous solution. The long and tortuous path leading to the first observations of ROA in biomolecules in 1989, in which the author was closely involved from the very beginning, is documented, followed by a survey of subsequent developments and applications up to the present day. Among other things, ROA provides information about motif and fold, as well as secondary structure, of proteins; solution structure of carbohydrates; polypeptide and carbohydrate structure of intact glycoproteins; new insight into structural elements present in unfolded protein sequences; and protein and nucleic acid structure of intact viruses. Quantum chemical simulations of observed Raman optical activity spectra provide the complete three-dimensional structure, together with information about conformational dynamics, of smaller biomolecules. Biomolecular ROA measurements are now routine thanks to a commercial instrument based on a novel design becoming available in 2004.

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“…It had long been appreciated that extending natural optical activity into the vibrational spectrum could provide more detailed and reliable stereochemical information because a vibrational spectrum contains many more bands sensitive to the details of the molecular structure (3N-6 fundamentals, where N is the number of atoms) [2]. This was finally achieved in the early 1970s when vibrational optical activity was first observed in small chiral molecules in fluid media using two complementary techniques: a circular polarization dependence of vibrational Raman scattering of visible laser light [85], and circular dichroism of infrared radiation [86]. These are now known as Raman optical activity (ROA) and vibrational circular dichroism (VCD), respectively [2,81,82].…”

Section: Vibrational Optical Activitymentioning

confidence: 99%

An Introduction to Chirality at the Nanoscale

Barron

2009

Chirality at the Nanoscale

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Infrared circular dichroism of carbon-hydrogen and carbon-deuterium stretching modes. Observations

Cited by 285 publications

References 0 publications

Characterizing vibrational motion beyond internal coordinates

Characterizing vibrational motion beyond internal coordinates

The development of biomolecular Raman optical activity spectroscopy

An Introduction to Chirality at the Nanoscale

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