Search results for "VIBRATION"

Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets

2010

The harmonic and anharmonic frequencies of fundamental vibrations in formaldehyde and water were successfully estimated using the B3LYP Kohn-Sham limit. The results obtained with polarization- and correlation-consistent basis sets were fitted with a two-parameter formula. Anharmonic corrections were obtained by a second order perturbation treatment (PT2). We compared the performance of the PT2 scheme on the two title molecules using SCF, MP2 and DFT (BLYP, B3LYP, PBE and B3PW91 functionals) methods combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) basis sets, Dunning’s basis sets (aug)-cc-pVXZ where X = D, T, Q, 5, 6 and Pople’s basis sets up to 6-311++G(3df,2pd). The influence…

HEALTH MONITORING, FAULT DETECTION AND DIAGNOSIS IN INDUSTRIAL ROTATING MACHINERY BY ADVANCED VIBRATION ANALYSIS

Vibrational circular dichroism studies of exceptionally strong chirality inducers in liquid crystals.

2021

7,7′-Disubstituted 2,2′-methylenedioxy-1,1′-binaphthyls are highly efficient chirality inducers in nematic liquid crystals. The absolute configuration of these compounds is, however, hard to determine as they only crystallize as racemic mixtures. In this work a Vibrational Circular Dichroism (VCD) study is reported that provides an unambiguous determination of the absolute configuration of these compounds. An in-depth General Coupled Oscillator (GCO) analysis of the source of the VCD signal reveals that the unusual structure of these binaphthyl compounds inherently leads to strong and robust VCD bands. Combined with linear transit calculations, our VCD studies allow for the determination of…

Analysis of Vibrational Circular Dichroism Spectra of Peptides

2020

Vibrational circular dichroism (VCD) is one of the major spectroscopic tools to study peptides. Nevertheless, a full understanding of what determines the signs and intensities of VCD bands of these compounds in the amide I and amide II spectral regions is still far from complete. In the present work, we study the origin of these VCD signals using the general coupled oscillator (GCO) analysis, a novel approach that has recently been developed. We apply this approach to the ForValNHMe model peptide in both α-helix and β-sheet configurations. We show that the intense VCD signals observed in the amide I and amide II spectral regions essentially have the same underlying mechanism, namely, the th…

Vibrational circular dichroism spectroscopy for probing the expression of chirality in mechanically planar chiral rotaxanes

2020

Mechanically interlocked molecules can exhibit molecular chirality that arises due to the mechanical bond rather than covalent stereogenic units. Developing applications of such systems is made challenging by the absence of techniques for assigning the absolute configuration of products and methods to probe how the mechanical stereogenic unit influences the spatial arrangements of the functional groups in solution. Here we demonstrate for the first time that Vibrational Circular Dichroism (VCD) can be used to not only discriminate between mechanical stereoisomers but also provide detailed information on their (co)conformations. The latter is particularly important as these molecules are now…

Self-Assembly of Supramolecular Polymers of N-Centered Triarylamine Trisamides in the Light of Circular Dichroism: Reaching Consensus between Electro…

2020

The self-assembly of chiral supramolecular polymers is an intricate process that spans a wide range of length scales. Circular dichroism techniques are ideal to study this process as they provide information on the molecular scale but are at the same time also sensitive probes of the long-range interactions that control the growth and morphology of these polymers. As yet, Electronic Circular Dichroism that uses electronic transitions as a probe has by far been the method of choice while Vibrational Circular Dichroism, which uses vibrational transitions to probe structure, is much less employed. Here, we report experimental and theoretical studies of the self-assembly of helical supramolecul…

Le vibrazioni in campo ferroviario: analisi f.e.m. dell’interazione convoglio-sovrastruttura-terreno

2003

This paper describes the formulation and application of a finite element method model that simulates the generation and propagation of train-induced vibrations into track-ground system. The F.E.M. model accounts for the interaction between ground, railway, shape of cross-section and train speed. The aim of this research is the evaluation of the influence of each factor on vibrational phenomena.

A quantum vocal theory of sound

2020

Concepts and formalism from acoustics are often used to exemplify quantum mechanics. Conversely, quantum mechanics could be used to achieve a new perspective on acoustics, as shown by Gabor studies. Here, we focus in particular on the study of human voice, considered as a probe to investigate the world of sounds. We present a theoretical framework that is based on observables of vocal production, and on some measurement apparati that can be used both for analysis and synthesis. In analogy to the description of spin states of a particle, the quantum-mechanical formalism is used to describe the relations between the fundamental states associated with phonetic labels such as phonation, turbule…

Molecular equilibrium structures from experimental rotational constants and calculated vibration–rotation interaction constants

2002

A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B(0) and sums of ab initio vibration-rotation interaction constants alpha(r)(B). The vibration-rotation interaction constants have been calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree-Fock vibration-rotation interaction constants have an accuracy similar to that obtained by a dir…

Optimized substrates and measurement approaches for Raman spectroscopy of graphene nanoribbons

2019

The on-surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. In this contribution, we use Raman spectroscopy to characterize different types of GNRs on their growth substrate and to track their quality upon substrate transfer. We present a Raman-optimized (RO) device substrate and an optimized mapping approach that allows for acquisition of high-resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substra…