ترغب بنشر مسار تعليمي؟ اضغط هنا

Overcoming the challenges in controlled thermal deposition of organic diradicals

115   0   0.0 ( 0 )
 نشر من قبل Maria Benedetta Casu
 تاريخ النشر 2020
  مجال البحث فيزياء
والبحث باللغة English




اسأل ChatGPT حول البحث

We have demonstrated that it is possible to evaporate diradicals in a controlled environment obtaining thin films in which the diradical character is preserved. However, evaporation represents a challenge. The presence of two radical sites makes the molecules more reactive, even in case of very stable single radicals. We have explored the parameters that play a role in this phenomenon. Bulk formation thermodynamics and delocalisation of the unpaired electrons play the major role. The higher the formation energies of the crystal, the more difficult is the evaporation of intact radicals. The larger the delocalization, the more stable is the film exposed to air. The evaporation of different radicals, also with a larger number of radical sites can be successfully addressed considering our findings.

قيم البحث

اقرأ أيضاً

Combining first-principles density functional theory simulations with IR and Raman experiments, we determine the frequency shift of vibrational modes of CO2 when physiadsorbed in the iso-structural metal organic framework materials Mg-MOF74 and Zn-MO F74. Surprisingly, we find that the resulting change in shift is rather different for these two systems and we elucidate possible reasons. We explicitly consider three factors responsible for the frequency shift through physiabsorption, namely (i) the change in the molecule length, (ii) the asymmetric distortion of the CO$_2$ molecule, and (iii) the direct influence of the metal center. The influence of each factor is evaluated separately through different geometry considerations, providing a fundamental understanding of the frequency shifts observed experimentally.
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal transport can be still described by phonons in metal-organic frameworks. Here, by studying two typical systems, i.e., crystal zeolitic imidazolate framework-4 (cZIF-4) and crystal zeolitic imidazolate framework-62 (c-ZIF62), we prove that the ultralow thermal conductivity in metal-organic frameworks is resulting from the strong phonon intrinsic structure scattering due to the large mass difference and the large cavity between Zn and N atoms. Our mean free path spectrum analysis shows that both propagating and non-propagating anharmonic vibrational modes exist in the systems, and contribute largely to the thermal conductivity. The corresponding weakly negative or positive temperature dependence of the thermal conductivity is stemming from the competition between the propagating and non-propagating anharmonic vibrational modes. Our study here provides a fundamental understanding of thermal transport in metal-organic frameworks and will guide the design of the thermal-related applications using metal-organic frameworks, e.g., inflammable gas storage, chemical catalysis, solar thermal conversion and so on.
Nanopores of nanometer-size holes are very promising devices for many applications: DNA sequencing, sensory, biosensoring and molecular detectors, catalysis and water desalination. These applications require accurate control over nanopores size. We r eport computer simulation studies of regrowth and healing of graphene nanopores of different sizes ranging from 30 to 5 {AA}. We study mechanism, speed of nanopores regrowth and structure of healed areas in the wide range of temperatures. We report existence of at least two distinct healing mechanisms, one so called edge attachment where carbons are attached to the edges of graphene sheet and another mechanism that involves atom insertion directly into a sheet of graphene even in the absence of the edges. These findings point a significantly more complicated pathways for graphene annealing. They also provide an important enabling step in development of graphene based devices for numerous nanotechnology applications.
We develop two new amphiphilic molecules that are shown to act as efficient surfactants for carbon nanotubes in non-polar organic solvents. The active conjugated groups, which are highly attracted to graphene nanotube surface, are based on pyrene and porphyrin. We show that relatively short (C18) carbon tails are insufficient to provide stabilization. As our ultimate aim is to disperse and stabilize nanotubes in siloxane matrix (polymer and crosslinked elastomer), both surfactant molecules were made with long siloxane tails to facilitate solubility and steric stabilization. We show that pyrene-siloxane surfactant is very effective in dispersing multi-wall nanotubes, while the porphyrin-siloxane is making single-wall nanotubes soluble, both in petroleum ether and in siloxane matrix.
Herein we employed high-resolution spectroscopic techniques in combination with periodic ab initio density functional theory (DFT) calculations to establish the different polarization processes for a porous copper-based MOF, termed HKUST-1. We used a lternating current measurements to determine its dielectric response between 4 Hz and 1.5 MHz where orientational polarization is predominant, while synchrotron infrared (IR) reflectance was used to probe the far-IR, mid-IR, and near-IR dielectric response across the 1.2 THz to 150 THz range (ca. 40 - 5000 cm^-1) where vibrational and optical polarizations are principal contributors to its dielectric permittivity. We demonstrate the role of pressure on the evolution of broadband dielectric response, where THz vibrations reveal distinct blue and red shifts of phonon modes from structural deformation of the copper paddle-wheel and the organic linker, respectively. We also investigated the effect of temperature on dielectric constants in the MHz region pertinent to microelectronics, to study temperature-dependent dielectric losses via dissipation in an alternating electric field. The DFT calculations offer insights into the physical mechanisms responsible for dielectric transitions observed in the experiments and enable us to explain the frequency shifts phenomenon detected under pressure. Together, the experiments and theory have enabled us to glimpse into the complex dielectric response and mechanisms underpinning a prototypical MOF subject to pressure, temperature, and vast frequencies.
التعليقات
جاري جلب التعليقات جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
mircosoft-partner

هل ترغب بارسال اشعارات عن اخر التحديثات في شمرا-اكاديميا