The dosimetry of neutron fields of therapeutic complex based on the U-120 cyclotron

In this work, the characteristics of the treat beam's dosimetry of fast neutrons of the U-120 cyclotron have been analyzed with the help of the ionizing method. The fast neutrons with 6, 3 MeV as medium energy have been obtained in coordination of deuterons with the target made of beryllium and are meant to be used for treating the patients with malignant neoplasms. The capacity of the dose in the beam of fast neutrons has been measured by ionization chambers of different types. The research has been done with the consideration of co-occurring gamma rays. The monitoring indices needed for calculation the duration of therapy session at given therapy dose have also been specified

Optical properties of the dibenzothiazolylphenol molecular crystals through ONIOM calculations: the effect of the electrostatic embedding scheme

Periodic density functional theory (DFT) and hybrid ONIOM time-dependent DFT/MM cluster calculations have been carried out to investigate the ground- and excited-state properties of the crystalline structures of the enolic and ketonic tautomeric forms of a propoxy-substituted dibenzothiazolylphenol molecule (OPr), a prototype for systems undergoing the excited-state intramolecular proton transfer process. The crystalline structures of the tautomeric forms are well reproduced and, as expected, at the ground state, the enol polymorph is predicted to be more stable than the keto one. At the excited state, the effect of the environment on time-dependent DFT calculations has been accounted for by including a charge embedding scheme, and the influence of different kinds of point charges (Mulliken, CM5, RESP and QEq) in determining the optical properties of the central molecule has been investigated. The results reveal that, in fair agreement with experimental data, the absorption (emission) energies of the enol (keto) OPr molecule is red-shifted of about 3 (3) nm going from the gas phase to chloroform and blue-shifted of 10 (23) nm going from the gas to the crystal phase when the electronic embedding with Mulliken charges is employed. The electrostatic embedding influences the excited-state properties more severely than the ground-state properties, and apart the QEq charges, all other models provide Stokes shifts in reasonable agreement with experimental data

Nonempirical Double-Hybrid Functionals: An Effective Tool for Chemists

Density functional theory (DFT) emerged in the last two decades as the most reliable tool for the description and prediction of properties of molecular systems and extended materials, coupling in an unprecedented way high accuracy and reasonable computational cost. This success rests also on the development of more and more performing density functional approximations (DFAs). Indeed, the Achilles’ heel of DFT is represented by the exchange-correlation contribution to the total energy, which, being unknown, must be approximated. Since the beginning of the 1990s, global hybrids (GH) functionals, where an explicit dependence of the exchange-correlation energy on occupied Kohn–Sham orbitals is introduced thanks to a fraction of Hartree–Fock-like exchange, imposed themselves as the most reliable DFAs for chemical applications. However, if these functionals normally provide results of sufficient accuracy for most of the cases analyzed, some properties, such as thermochemistry or dispersive interactions, can still be significantly improved. A possible way out is represented by the inclusion, into the exchange-correlation functional, of an explicit dependence on virtual Kohn–Sham orbitals via perturbation theory. This leads to a new class of functionals, called double-hybrids (DHs). In this Account, we describe our nonempirical approach to DHs, which, following the line traced by the Perdew–Burke–Ernzerhof approach, allows for the definition of a GH (PBE0) and a DH (QIDH) model. In such a way, a whole family of nonempirical functionals, spanning on the highest rungs of the Perdew’s quality scale, is now available and competitive with other—more empirical—DFAs. Discussion of selected cases, ranging from thermochemistry and reactions to weak interactions and excitation energies, not only show the large range of applicability of nonempirical DFAs, but also underline how increasing the number of theoretical constraints parallels with an improvement of the DFA’s numerical performances. This fact further consolidates the strong theoretical framework of nonempirical DFAs. Finally, even if nonempirical DH approaches are still computationally expensive, relying on the fact that they can benefit of all technical enhancements developed for speeding up post-Hartree–Fock methods, there is substantial hope for their near future routine application to the description and prediction of complex chemical systems and reactions.This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 648558)

Emissive Azobenzenes Delivered on a Silver Coordination Polymer

International audienceAzobenzene has become a ubiquitous component of functional molecules and polymeric materials because of the light-induced trans → cis isomerization of the diazene group. In contrast, there are very few applications utilizing azobenzene luminescence, since the excitation energy typically dissipates via nonradiative pathways. Inspired by our earlier studies with 2,2′-bis[N,N′-(2-pyridyl)methyl]diaminoazobenzene (AzoAMoP) and related compounds, we investigated a series of five aminoazobenzene derivatives and their corresponding silver complexes. Four of the aminoazobenzene ligands, which exhibit no emission under ambient conditions, form silver coordination polymers that are luminescent at room temperature. AzoAEpP (2,2′-bis[N,N′-(4-pyridyl)ethyl]diaminoazobenzene) assembles into a three-dimensional coordination polymer (AgAAEpP) that undergoes a reversible loss of emission upon the addition of metal-coordinating analytes such as pyridine. The switching behavior is consistent with the disassembly and reassembly of the coordination polymer driven by displacement of the aminoazobenzene ligands by coordinating analytes

Modeling emission features of salicylidene aniline molecular crystals: A QM/QM' approach

A new computational protocol relying on the use of electrostatic embedding, derived from QM/QM' ONIOM calculations, to simulate the effect of the crystalline environment on the emission spectra of molecular crystals is here applied to the beta-form of salicylidene aniline (SA). The first singlet excited states (S-1) of the SA cis-keto and trans-keto conformers, surrounded by a cluster of other molecules representing the crystalline structure, were optimized by using a QM/QM' ONIOM approach with and without electronic embedding. The model system consisting of the central salicylidene aniline molecule was treated at the DFT level by using either the B3LYP, PBE0, or the CAM-B3LYP functional, whereas the real system was treated at the HF level. The CAM-B3LYP/HF level of theory provides emission energies in good agreement with experiment with differences of 220/232 nm (cis-keto form) and 28/214 nm (trans-keto form), respectively, whereas notably larger differences are obtained using global hybrids. Though such differences on the optical properties arise from the density functional choice, the contribution of the electronic embedding is rather independent of the functional used. This plays in favor of a more general applicability of the present protocol to other crystalline molecular systems

Effect of Polymer Composition on the Optical Properties of a New Aggregation-Induced Emission Fluorophore:A Combined Experimental and Computational Approach

Nowadays, fluorophores with a tetraphenylethylene (TPE) core are considered interesting due to the aggregation-induced emission (AIE) behavior that enables their effective use in polymer films. We propose a novel TPE fluorophore (TPE-BPAN) bearing two dimethylamino push and a 4-biphenylacetonitrile pull moieties with the typical AIE characteristics in solution and in the solid state, as rationalized by DFT calculations. Five different host polymer matrices with different polarity have been selected: two homopolymers of poly(methylmethacrylate) (PMMA) and poly(cyclohexyl methacrylate) (PCHMA) and three copolymers at different compositions (P(MMA-co-CHMA) 75:25, 50:50, and 25:75 mol%). The less polar comonomer of CHMA appeared to enhance TPE-BPAN emission with the highest quantum yield (QY) of about 40% measured in P(MMA-co-CHMA) 75:25. Further reduction in polymer polarity lowered QY and decreased the film stability and adhesion to the glass surface. LSC performances were not significantly affected by the matrix’s polarity and resulted in around one-third of the state-of-the-art due to the reduced QY of TPE-BPAN. The theoretical investigation based on density functional theory (DFT) calculations clarified the origin of the observed AIE and the role played by the environment in modulating the photophysical behavior.</p

Transition-metal-free a-arylation of enolizable aryl ketones and mechanistic evidence for a radical process

The a-arylation of enolizable aryl ketones can be carried out with aryl halides under transition-metal-free conditions using KOtBu in DMF. The a-aryl ketones thus obtained can be used for step- and cost-economic syntheses of fused heterocycles and Tamoxifen. Mechanistic studies demonstrate the synergetic role of base and solvent for the initiation of the radical process

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022