Search results for "Molecular vibration"
showing 10 items of 112 documents
Hexacarbonyls of Mo, W, and Sg: Metal–CO Bonding Revisited
2017
Calculations of the first bond dissociation energies (FBDEs) and other molecular properties of M(CO)6, where M = Mo, W, and Sg, have been performed using a variety of nonrelativistic and relativistic methods, such as ZORA-DFT, X2c+AMFI-CCSD(T), and Dirac–Coulomb density functional theory. The aim of the study is to assist experiments on the measurements of the FBDE of Sg(CO)6. We have found that, different from the results published earlier, the metal–CO bond in Sg(CO)6 should be weaker than that in W(CO)6. A comparison of the relativistic and nonrelativistic FBDE values, as well as molecular orbital and vibrational frequency analyses within both the nonrelativistic and relativistic approac…
Effect of molecular Stokes shift on polariton dynamics
2021
When the enhanced electromagnetic field of a confined light mode interacts with photoactive molecules, the system can be driven into the regime of strong coupling, where new hybrid light-matter states, polaritons, are formed. Polaritons, manifested by the Rabi split in the dispersion, have shown potential for controlling the chemistry of the coupled molecules. Here, we show by angle-resolved steady-state experiments accompanied by multi-scale molecular dynamics simulations that the molecular Stokes shift plays a significant role in the relaxation of polaritons formed by organic molecules embedded in a polymer matrix within metallic Fabry-Pérot cavities. Our results suggest that in the case …
Vibronic Model for Intercommunication of Localized Spins via Itinerant Electron
2019
In this article, we propose a vibronic pseudo Jahn–Teller model for partially delocalized mixed-valence molecules aimed to describe the magnetic coupling between the localized spins mediated by the delocalized electron. The simplest partially delocalized system that retains the main studied features is assumed to consist of a one-electron mixed-valence dimer, which is connected to the two terminal magnetic ions. The model involves the following key interactions: electron transfer in the spin-delocalized subsystem of a mixed-valence molecule, which is mimicked by a dimeric unit, coupling of the itinerant electrons with the molecular vibrations, and isotropic magnetic exchange between the loc…
Influence of the exchange and correlation functional on the structure of amorphous InSb and In3SbTe2 compounds
2016
We have investigated the structural, vibrational, and electronic properties of the amorphous phase of InSb and In3SbTe2 compounds of interest for applications in phase change non-volatile memories. Models of the amorphous phase have been generated by quenching from the melt by molecular dynamics simulations based on density functional theory. In particular, we have studied the dependence of the structural properties on the choice of the exchange-correlation functional. It turns out that the use of the Becke-Lee-Yang-Parr functional provides models with a much larger fraction of In atoms in a tetrahedral bonding geometry with respect to previous results obtained with the most commonly used P…
A Universal Length-Dependent Vibrational Mode in Graphene Nanoribbons
2019
Graphene nanoribbons (GNRs) have attracted considerable interest as their atomically tunable structure makes them promising candidates for future electronic devices. However, obtaining detailed information about the length of GNRs has been challenging and typically relies on low-temperature scanning tunneling microscopy. Such methods are ill-suited for practical device application and characterization. In contrast, Raman spectroscopy is a sensitive method for the characterization of GNRs, in particular for investigating their width and structure. Here, we report on a length-dependent, Raman active low-energy vibrational mode that is present in atomically precise, bottom-up synthesized armch…
Surface charges at the CaF2/water interface allow very fast intermolecular vibrational-energy transfer
2020
Abstract We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface‐specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D2O) molecules and provide information about the sub‐picosecond vibrational‐energy‐relaxation dynamics at the buried solid/liquid interface. We find that strongly H‐bonded OD groups, with a vibrational frequency below 2500 cm−1, display very rapid spectral diffusion and vibrational relaxation; for weakly H‐bonded OD groups, above 2500 cm−1, the dynamics slows down substantially. Atomistic simulations based on electronic‐structu…
Irradiation effects on the OH-related infrared absorption band in synthetic wet silica.
2007
The effects of b-irradiation on the OH-related infrared (IR) absorption band in synthetic wet silica samples have been investigated by Fourier transform infrared spectroscopy. Depending on the accumulated doses, b-irradiation affects different zones of the IR composite band at about 3670 cm 1 , assigned to the OH stretching modes of silanol groups. These modifications are independent of the original OH content. The results are discussed considering possible radiation-induced changes of the silanol bonding configuration and of the glass network. These are monitored by revealing the IR band a 2260 cm 1 , which is related to the distribution of Si–O–Si bond angle. We have identified the existence of…
Temperature effects on the IR absorption bands of hydroxyl and deuteroxyl groups in silica glass
2009
Abstract In this report we will show the changes of the band shape of the hydroxyl group (SiOH) infrared (IR) absorption band (∼3670 cm −1 ) in silica glass induced by lowering temperature in the range from 290 to 20 K. This band is considered as the overlap of several spectral components associated to the vibrational activity of hydroxyl groups in different bond configurations. By a suitable analysis of the experimental band profile in terms of different sub-bands, we studied the thermal evolution of each component and we reconsidered their assignations. For comparison we examined the SiOD absorption band (∼2710 cm −1 ) as a function of temperature as well. Our data can be interpreted as a…
The Boson Peak of Amyloid Fibrils: Probing the Softness of Protein Aggregates by Inelastic Neutron Scattering
2014
Proteins and polypeptides are characterized by low-frequency vibrations in the terahertz regime responsible for the so-called "boson peak". The shape and position of this peak are related to the mechanical properties of peptide chains. Amyloid fibrils are ordered macromolecular assemblies, spontaneously formed in nature, characterized by unique biological and nanomechanical properties. In this work, we investigate the effects of the amyloid state and its polymorphism on the boson peak. We used inelastic neutron scattering to probe low-frequency vibrations of the glucagon polypeptide in the native state and in two different amyloid morphologies in both dry and hydrated sample states. The dat…
FT Raman and DFT Study on a Series of All-antiOligothienoacenes End-Capped with Triisopropylsilyl Groups
2009
minal a positions. These substituents aid in purification and solution processability, and can be removed under mild chemical conditions. For the first time, we have the opportunity to analyze a series of oligothienoacenes to gain insight into the fundamental structure–property relationships with respect to the addition of each ring. Furthermore, this series of compounds can be directly compared to other well-studied series of closely related oligomers, such as nonfused oligothiophenes and fully fused all-syn oligothienoacenes. [7] To gain precise insight into relationships between the structure and properties of a wide range of p-conjugated molecular Herein, we study the p-conjugational pr…