Raman Optical Activity of Methyloxirane Gas and Liquid

Šebestı́k, Jaroslav; Bouř, Petr

doi:10.1021/jz200108v

Cited by 79 publications

(75 citation statements)

References 42 publications

(51 reference statements)

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“…Also the evaluated relative intensities match the measured ones very well. For instance, the strong experimental band between 1200 and 1300 cm −1 , which, according to static calculations, corresponds to C-H bending and C-CH 2 stretching vibrations and is by far the most intense one in the experimental gas-phase spectrum of S-methyloxirane, 34,94 is perfectly reproduced in the calculations. This is especially true in case of BP86, where the shift to lower wavenumbers is less pronounced than in case of BLYP.…”

Section: Comparison To Experimental Datamentioning

confidence: 62%

“…Nevertheless, the agreement is very good, especially if compared to experimental data of S-methyloxirane vapor that show the most intense bands at around 960 and 1270 cm −1 . 34,94 Even a tiny broadening at the higher-wavenumber side of the experimental band at about 745 cm −1 is obtained for the corresponding band in the calculation employing BP86. With BLYP, this band occurs with a relatively small intensity between the two strong bands at 686 and 768 cm −1 .…”

Section: Parameter Dependence Of the Raman Spectramentioning

confidence: 90%

“…34, 52, and [89][90][91][92][93][94][95]. Nevertheless, to the best of our knowledge, no computational study of the Raman spectrum of its liquid phase has been published yet.…”

Section: Parameter Dependence Of the Raman Spectramentioning

confidence: 99%

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Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Luber

Iannuzzi

Hutter

2014

The Journal of Chemical Physics

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We describe the calculation of Raman spectra for periodic systems via ab initio molecular dynamics (AIMD) utilizing the Gaussian and plane wave method in the program package CP2K. The electric-dipole–electric-dipole polarizability tensor has been implemented for an arbitrary shape of the simulation cell. In addition, a computationally efficient approach for its decomposition into local contributions is presented. As an example for the application of computational Raman spectroscopy to liquids, the Raman spectra of S-methyloxirane in the liquid phase have been calculated together with Raman spectra obtained from static calculations employing the double-harmonic approximation. The comparison to experimental data illustrates that a very good agreement between experiment and simulated spectra can be obtained employing AIMD, which takes into account anharmonicities and dynamical effects at ambient conditions.

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Section: Comparison To Experimental Datamentioning

confidence: 62%

Section: Parameter Dependence Of the Raman Spectramentioning

confidence: 90%

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Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Luber

Iannuzzi

Hutter

2014

The Journal of Chemical Physics

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“…32,33 The calculations were performed with the B3LYP hybrid exchange-correlation functional [34][35][36] because of its good performance for ROA calculations 25,26,[37][38][39][40] . In order to have a good description of the dispersion interactions, we employed the D2 dispersion correction of Grimme.…”

Section: Computational Detailsmentioning

confidence: 99%

Where does the Raman optical activity of [Rh(en)₃]³⁺ come from? Insight from a combined experimental and theoretical approach

Humbert-Droz

Oulevey

Daku

et al. 2014

Phys. Chem. Chem. Phys.

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Backscattered Raman optical activity (ROA) spectra are measured for Δ-and Λ-tris-(ethylenediamine)rhodium( chloride in aqueous solution. In addition, the spectra of the four possible conformers in the Λ configuration are investigated by ab initio calculations. The Λ() conformer is in best agreement with experimental spectra and examined in more details. The two most stable conformers according to the calculations are not compatible with the experimental ROA spectrum. Insights into the origin of observed band intensities are obtained by means of group coupling matrices. The influence of the first solvation shell is explored via an ab initio molecular dynamics simulation. Taking explicit solvent molecules into account further improves the agreement between calculation and experiment. Analysis of selected normal modes using group coupling matrices shows that solvent molecules lead to normal mode rotation and thus contribute to the ROA intensity, whereas the contribution of the Rh can be neglected.

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“…48,49 The geometry of methyloxirane is optimized at the B3LYP/aug-cc-pvTV computation level, which has been used by previous works. 50 Using the optimized ground state of the molecule, the response tensors were calculated using the same basis. Throughout the article, these molecular response tensors are evaluated with respect to the coordinate origin.…”

Section: Analytical Theory Ofmentioning

confidence: 99%

Strongly Enhanced Raman Optical Activity in Molecules by Magnetic Response of Nanoparticles

Zhang

Wang

et al. 2016

J. Phys. Chem. C

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An analytical theory for the surface-enhanced Raman optical activity (SEROA) with the magnetic response of the substrate particle has been presented. We have demonstrated that the SEROA signal is proportional to the magnetic polarizability of the substrate particle, which can be significantly enhanced due to the existence of the magnetic response. At the same time, a large circular intensity difference (CID) for the SEROA can also be achieved in the presence of the magnetic response. Taking Si nanoparticles as examples, we have found that the CID enhanced by a Si nanoparticle is 10 times larger than that of Au. Furthermore, when the molecule is located in the hotspot of a Si dimer, CID can be 60 times larger. The phenomena originate from large magnetic fields concentrated near the nanoparticle and boosted magnetic dipole emission of the molecule.The symmetric breaking of the electric fields caused by the magnetic dipole response of the nanoparticle also plays an important role. Our findings provide a new way to tailor the Raman optical activity by designing metamaterials with the strong magnetic response. I.INTRODUCTIONChirality plays a crucial role in modern biochemistry and the evolution of life. 1 Many biologically active molecules are chiral, detection and quantification of chiral enantiomers of these biomolecules are of considerable importance. In the past years, many spectroscopic techniques have been proposed for the determination of the molecule chirality, including electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity spectroscopy (ROA). [2][3][4] Among all these techniques, Raman optical activity spectroscopy (ROA) is a powerful method, 5 because this technique can give the chirality related to the structural information of all parts of the molecule and be particularly sensitive to the conformation and dynamics of biological molecules. 6,7 For example, the ROA has been proved to be useful in characterizing secondary order structures of proteins, 8 determining the absolute configurations of small chiral molecules, 9 and studying the dynamics of biomolecules. 10 However, the widely use of the ROA technique is hampered by the weakness of signal intensities, which is always 3 orders of magnitude smaller than its parent Raman intensities. [4][5][6][7][8][9][10][11] Usually long measuring times and densely concentrated samples are required to guarantee the reliability of the measurement. How to improve the detection efficiency with the ROA technique becomes a key problem in recent years. Many studies focused on the surface enhanced Raman optical activity (SEROA) based on metal surface plasmon resonances. [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] This is because the Raman scattering from molecules placed near metal surfaces can be strongly enhanced, giving rise to surface-enhanced Raman scattering (SERS). 31 The typical enhancement factor of the SERS is about 7 10 and can reach 1 4 1 0 under favorable conditions. ...

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Raman Optical Activity of Methyloxirane Gas and Liquid

Cited by 79 publications

References 42 publications

Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Where does the Raman optical activity of [Rh(en)₃]³⁺ come from? Insight from a combined experimental and theoretical approach

Strongly Enhanced Raman Optical Activity in Molecules by Magnetic Response of Nanoparticles

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Raman Optical Activity of Methyloxirane Gas and Liquid

Cited by 79 publications

References 42 publications

Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Where does the Raman optical activity of [Rh(en)3]3+ come from? Insight from a combined experimental and theoretical approach

Strongly Enhanced Raman Optical Activity in Molecules by Magnetic Response of Nanoparticles

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Where does the Raman optical activity of [Rh(en)₃]³⁺ come from? Insight from a combined experimental and theoretical approach