scholarly journals On the SN2 reactions modified in vibrational strong coupling experiments: reaction mechanisms and vibrational mode assignments

2020 ◽  
Vol 22 (41) ◽  
pp. 23545-23552
Author(s):  
Clàudia Climent ◽  
Johannes Feist
Keyword(s):  
Strong Coupling ◽  
Reaction Mechanisms ◽  
Vibrational Mode ◽  
Vibrational Modes ◽  
Sn2 Reactions

We study the mechanism of SN2 reactions modified in vibrational strong coupling experiments and propose a new assignment of the vibrational modes.

scholarly journals Reply to the Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments”

2021 ◽  
Author(s):  
Clàudia Climent ◽  
Johannes Feist
Keyword(s):  
Strong Coupling ◽  
Reaction Mechanisms ◽  
Vibrational Mode ◽  
Chem Phys ◽  
Sn2 Reactions ◽  
Original Manuscript ◽  
Supplementary Material ◽  
Phys Chem Chem Phys

<div> <div> <div> <p> </p><div> <div> <div> <p>In September 2020, we became aware that a comment (A. Thomas, L. Lethuillier-Karl, J. Moran and T. Ebbesen, 2020, DOI:10.26434/chemrxiv.12982358.v1.) on our recent paper (C. Climent and J. Feist, Phys. Chem. Chem. Phys., 2020, 22, 23545) had been posted to ChemRxiv. Since our attempts in October 2020 to reach out to the authors to discuss the points they raised did not receive a response as of April 2021, and the comment was not submitted as a formal comment to the original journal either, we here provide a brief reply based on the results that were already reported in our original manuscript. Most importantly, we show that we did not “presumably overlook” any data in the supplementary material of their original article, but that our results are actually fully consistent with those data. </p> </div> </div> </div> </div> </div> </div>

scholarly journals Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments"

2020 ◽  
Author(s):  
Anoop Thomas ◽  
Lucas Lethuillier-Karl ◽  
Joseph Moran ◽  
Thomas Ebbesen
Keyword(s):  
Reaction Mechanisms ◽  
Recent Article ◽  
Cavity Mode ◽  
Vibrational Mode ◽  
Theoretical Studies ◽  
Vibrational Modes ◽  
Experimental Proof ◽  
Sn2 Reactions ◽  
Vibrational Bands ◽  
Supplementary Material

We welcome the large number of theoretical studies to analyze our experiments on chemistry under VSC. As Climent and Feist state in their recent article, many details are not understood. 1 However, there should be no need to misrepresent our results. In their paper, the authors re-analyze, not the chemistry under VSC, but the reactions that we used that have been studied for over half a century and for which there is no consensus about the details of the mechanism. 2 Secondly, they try to assign the vibrational bands of the reactants. Indeed, as they find, they are often mixed (coupled vibrational modes). For simplicity, it is commonplace in chemistry to describe vibrations according to their main contribution, a convention that we follow in our papers. Since there are differences between our results and their calculations, they assume that our assignments are wrong. Finally, they conclude that we must have coupled the solvent, apparently by a higher cavity mode, despite the experimental proof to the contrary in the original paper.3 The proof that the solvent was not coupled is reproduced below for those who are interested, together with one example of an unequivocal assignment that was in the supplementary material, 4 which Climent and Feist presumably overlooked.

scholarly journals Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments"

2020 ◽  
Author(s):  
Anoop Thomas ◽  
Lucas Lethuillier-Karl ◽  
Joseph Moran ◽  
Thomas Ebbesen
Keyword(s):  
Reaction Mechanisms ◽  
Recent Article ◽  
Cavity Mode ◽  
Vibrational Mode ◽  
Theoretical Studies ◽  
Vibrational Modes ◽  
Experimental Proof ◽  
Sn2 Reactions ◽  
Vibrational Bands ◽  
Supplementary Material

We welcome the large number of theoretical studies to analyze our experiments on chemistry under VSC. As Climent and Feist state in their recent article, many details are not understood. 1 However, there should be no need to misrepresent our results. In their paper, the authors re-analyze, not the chemistry under VSC, but the reactions that we used that have been studied for over half a century and for which there is no consensus about the details of the mechanism. 2 Secondly, they try to assign the vibrational bands of the reactants. Indeed, as they find, they are often mixed (coupled vibrational modes). For simplicity, it is commonplace in chemistry to describe vibrations according to their main contribution, a convention that we follow in our papers. Since there are differences between our results and their calculations, they assume that our assignments are wrong. Finally, they conclude that we must have coupled the solvent, apparently by a higher cavity mode, despite the experimental proof to the contrary in the original paper.3 The proof that the solvent was not coupled is reproduced below for those who are interested, together with one example of an unequivocal assignment that was in the supplementary material, 4 which Climent and Feist presumably overlooked.

scholarly journals Reply to the Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments”

2021 ◽  
Author(s):  
Clàudia Climent ◽  
Johannes Feist
Keyword(s):  
Strong Coupling ◽  
Reaction Mechanisms ◽  
Vibrational Mode ◽  
Chem Phys ◽  
Sn2 Reactions ◽  
Original Manuscript ◽  
Supplementary Material ◽  
Phys Chem Chem Phys

<div> <div> <div> <p> </p><div> <div> <div> <p>In September 2020, we became aware that a comment (A. Thomas, L. Lethuillier-Karl, J. Moran and T. Ebbesen, 2020, DOI:10.26434/chemrxiv.12982358.v1.) on our recent paper (C. Climent and J. Feist, Phys. Chem. Chem. Phys., 2020, 22, 23545) had been posted to ChemRxiv. Since our attempts in October 2020 to reach out to the authors to discuss the points they raised did not receive a response as of April 2021, and the comment was not submitted as a formal comment to the original journal either, we here provide a brief reply based on the results that were already reported in our original manuscript. Most importantly, we show that we did not “presumably overlook” any data in the supplementary material of their original article, but that our results are actually fully consistent with those data. </p> </div> </div> </div> </div> </div> </div>

Synchrotron spectroscopy of the CSH-bending and CH3-rocking bands of methyl mercaptan

2020 ◽  
Vol 98 (6) ◽  
pp. 519-529
Author(s):  
R.M. Lees ◽  
E.M Reid ◽  
Li-Hong Xu ◽  
B.E. Billinghurst
Keyword(s):  
Ground State ◽  
Vibrational Mode ◽  
Good Representation ◽  
Methyl Mercaptan ◽  
Vibrational Modes ◽  
Oscillatory Structure ◽  
Out Of Plane ◽  
Type Character ◽  
Fourier Transform Spectra ◽  
Synchrotron Spectroscopy

The CSH-bending and CH3-rocking infrared bands of CH3SH have been investigated in Fourier transform spectra recorded at 0.001 cm−1 resolution employing synchrotron radiation at the Canadian Light Source in Saskatoon. The relative band strengths and structures are quite different from those of the CH3OH methanol analogue, with the CSH bend being very weak and both the in-plane and out-of-plane CH3 rocks being strong with intensities greater than the C–S stretch. The CSH bend has parallel a-type character with no detectable b-type component. The out-of-plane CH3 rock is a purely c-type perpendicular band, whereas the in-plane rock is of mixed a/b character. Sub-bands have been assigned for A and E torsional species up to about K = 10 for each vibrational mode, providing upper-state term values from which K-reduced substate origins were determined. For the CSH bend, the origins follow the customary oscillatory torsional pattern as a function of K with a sharply reduced amplitude of 0.362 cm−1 compared to the 0.653 cm−1 for the ground state. The torsional energy curves for the out-of-plane rock are also well-behaved but have inverted ordering of the A–E torsional splitting components and a larger amplitude of 1.33 cm−1. In contrast, the substate origins for the in-plane rock are scattered over a range of about 2 cm−1 without clear oscillatory structure. Several instances of coupling among the lower modes and the ground state via resonances between accidentally near-degenerate levels have been observed and characterized. Ab initio calculations are found to give a good representation of the frequency and relative intensity patterns for the lower vibrational modes.

An Analysis of Infrared Spectroscopic Geometries

1997 ◽  
Vol 477 ◽  
Author(s):  
Gregory T. Merklin ◽  
Huihong Luo ◽  
Christopher E. D. Chidsey
Keyword(s):  
Vibrational Mode ◽  
Signal To Noise Ratio ◽  
Signal Strength ◽  
Internal Reflection ◽  
Infrared Spectrometry ◽  
Vibrational Modes ◽  
Signal To Noise ◽  
Transmission Spectroscopy ◽  
Infrared Spectroscopic ◽  
Experimental Geometry

ABSTRACTThe influence of experimental geometry on the signal strength and signal-to-noise ratio of infrared spectrometry has been investigated. In general, it was found that the choice of optimum experimental geometry depended on the orientation of the vibrational mode being investigated. In particular, it has been calculated that internal reflection spectrometry is relatively insensitive to vibrational modes perpendicular to the surface relative to transmission spectroscopy at Brewster's angle, and this has been confirmed by experiment.

scholarly journals The Trivacancy and Trivacancy-Oxygen Family of Defects in Silicon

2013 ◽  
Vol 205-206 ◽  
pp. 181-190 ◽  
Author(s):  
Vladimir P. Markevich ◽  
Anthony R. Peaker ◽  
Bruce Hamilton ◽  
S.B. Lastovskii ◽  
Leonid I. Murin ◽  
...  
Keyword(s):  
Deep Level Transient Spectroscopy ◽  
Minority Carrier ◽  
Vibrational Mode ◽  
Deep Level ◽  
Vibrational Modes ◽  
Carrier Injection ◽  
Local Vibrational Mode ◽  
Diffusion Paths ◽  
Transient Spectroscopy ◽  
And Diffusion

The data obtained recently from combined deep-level-transient spectroscopy (DLTS), local vibrational mode (LVM) spectroscopy and ab-initio modeling studies on structure, electronic properties, local vibrational modes, reconfiguration and diffusion paths and barriers for trivacancy (V3) and trivacancy-oxygen (V3O) defects in silicon are summarized. New experimental results on the introduction rates of the divacancy (V2) and trivacancy upon 4 MeV electron irradiation and on the transformation of V3 from the fourfold coordinated configuration to the (110) planar one upon minority carrier injection are reported. Possible mechanisms of the transformation are considered and discussed.

Quantum Strong Coupling with Protein Vibrational Modes

2016 ◽  
Vol 7 (20) ◽  
pp. 4159-4164 ◽  
Author(s):  
Robrecht M. A. Vergauwe ◽  
Jino George ◽  
Thibault Chervy ◽  
James A. Hutchison ◽  
Atef Shalabney ◽  
...  
Keyword(s):  
Strong Coupling ◽  
Vibrational Modes

Prospects for Vibrational-Mode EELS with High Spatial Resolution

2014 ◽  
Vol 20 (3) ◽  
pp. 658-663 ◽  
Author(s):  
R.F. Egerton
Keyword(s):  
Energy Loss ◽  
Spatial Resolution ◽  
Cross Sections ◽  
High Spatial Resolution ◽  
Vibrational Mode ◽  
Oscillator Strengths ◽  
Vibrational Modes ◽  
Loss Peak ◽  
Scattering Process ◽  
Transmission Electron

AbstractTaking advantage of previous measurements by Geiger and co-workers, we discuss the possibilities and problems of measuring vibrational modes of energy loss in a transmission electron microscope fitted with a monochromator and a high-resolution energy-loss spectrometer. The tail of the zero-loss peak is seen to be a major limitation, rather than its full-width at half-maximum. Because of the low oscillator strengths and small cross-sections involved, radiation damage will limit the spatial resolution if this technique is applied to organic specimens. Delocalization of the inelastic scattering may also be a limitation, if a dipole description of the scattering process is valid.

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