Fluxional halogen bonds in linear complexes of tetrafluorodiiodobenzene with dinitrobenzene.

The fluxional nature of halogen bonds (XBs) in small molecular clusters, supramolecules, and molecular crystals has received considerable attention in recent years. In this work, based on extensive density-functional theory calculations and detailed electrostatic potential (ESP), natural bonding orbital (NBO), non-covalent interactions-reduced density gradient (NCI-RDG), and quantum theory of atoms in molecules (QTAIM) analyses, we unveil the existence of fluxional halogen bonds (FXBs) in a series of linear (IC6F4I)m(OONC6H4NOO)n (m + n = 2-5) complexes of tetrafluorodiiodobenzene with dinitrobenzene which appear to be similar to the previously reported fluxional hydrogen bonds (FHBs) in small water clusters (H2O)n (n = 2-6). The obtained GS ⇌ TS ⇌ GS ' $$ \mathrm{GS}\rightleftharpoons \mathrm{TS}\rightleftharpoons {\mathrm{GS}}^{\hbox{'}} $$ fluxional mechanisms involve one FXB in the systems which fluctuates reversibly between two linear CI···O XBs in the ground states (GS and GS') via a bifurcated CI O2N van der Waals interaction in the transition state (TS). The cohesive energies (Ecoh) of these complexes with up to four XBs exhibit an almost perfect linear relationship with the numbers of XBs in the systems, with the average calculated halogen bond energy of Ecoh/XB = 3.48 kcal·mol-1 in the ground states which appears to be about 55% of the average calculated hydrogen bond energy (Ecoh/HB = 6.28 kcal·mol-1) in small water clusters.

Restriction on molecular fluxionality by substitution: A case study for the 1,10-dicyanobullvalene.

We show herein that 1,10-dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10-dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born-Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long-time limit, isomerizations of the 14 isomers, each with Cs symmetry, approach the "14 Cs → C7v" thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C7v symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un-explored properties e.g. for the equilibration dynamics of C10H10.

VMFNet: visual-microwave dual-modality real-time target detection model for detecting damage to curved radar absorbing materials.

Damage to radar absorbing materials (RAMs) reduces the stealth capabilities and battlefield survivability of the equipment. Research on RAM damage detection technology is key to outfield equipment maintenance. In this paper, an intelligent RAM damage detection method based on visual and microwave modalities is proposed. A compressed sensing planar-scanning microwave imaging method based on a range migration algorithm (RMA) imaging operator and fast Gaussian gridding nonuniform fast Fourier transform (FGG-NUFFT) is proposed, achieving high imaging quality and speed. A dual-modality, curved RAM dataset (DCR dataset) is constructed, composed of visual images and microwave images showing two kinds of damage: round shedding and strip cracks. A new dual-modality target detection model, the visual-microwave fusion network (VMFNet), is designed to detect RAM damage. Its mean average precision (mAP) reaches 81.87%, and its inference speed reaches 35.91 fps. A visual network (VisNet) and microwave network (MicNet) are designed as the backbone of VMFNet for extracting the visual and microwave features of RAMs. A path aggregation network (PANet) unit is designed to fuse the multiscale features of the two modalities, resulting in good retention of shallow-level features and high detection accuracy. The head contains different receptive fields and outputs three scales of detection results, effectively detecting damage of different sizes.

Oven-Controlled MEMS Oscillator with Integrated Micro-Evaporation Trimming.

This study reports an oven-controlled microelectromechanical systems oscillator with integrated micro-evaporation trimming that achieves frequency stability over the industrial temperature range and permanent frequency trimming after vacuum packaging. The length-extensional-mode resonator is micro-oven controlled and doped degenerately with phosphorous to achieve a frequency instability of ±2.6 parts per million (ppm) in a temperature range of -40 to 85 °C. The micro-evaporators are bonded to the resonator, integrated face-to-face, and encapsulated in vacuum. During trimming, the micro-evaporators are heated electrically, and the aluminum layers on their surfaces are evaporated and deposited on the surface of the resonator that trims the resonant frequency of the resonator permanently. The impact of the frequency trimming on the temperature stability is very small. The temperature drift increases from ±2.6 ppm within the industrial temperature range before trimming to ±3.3 ppm after a permanent trimming of -426 ppm based on the local evaporation of Al. The trimming rate can be controlled by electric power. A resonator is coarse-trimmed by approximately -807 ppm with an evaporation power of 960 mW for 0.5 h, and fine-trimmed by approximately -815 ppm with an evaporation power of 456 mW for 1 h. Though the Q-factor decreases after trimming, a Q-factor of 304,240 is achieved after the trimming of -1442 ppm.

Superatomic icosahedral-CnB12-n (n = 0, 1, 2) Stuffed mononuclear and binuclear borafullerene and borospherene nanoclusters with spherical aromaticity.

Boron and boron-based nanoclusters exhibit unique structural and bonding patterns in chemistry. Extensive density functional theory calculations performed in this work predict the mononuclear walnut-like Ci C50B54 (1) (C2B10@C48B44), C1 C50B54 (2) (CB11@C49B43), and S10 C50B54 (3) (B12@C50B42) which contain one icosahedral-CnB12-n core (n = 0, 1, 2) at the center following the Wade's skeletal electron counting rules and the approximately electron sufficient binuclear peanut-like Cs C88B78 (4) ((C2B10)2@C84B58), Cs C88B78 (5) ((CB11)2@C86B56), Cs C88B78 (6) ((B12)2@C88B54), Cs B180 (7) ((B12)2@B156), Cs B182 (8) ((B12)2@B158), and Cs B184 (9) ((B12)2@B160) which encapsulate two interconnected CnB12-n icosahedrons inside. These novel core-shell borafullerene and borospherene nanoclusters appear to be the most stable species in thermodynamics in the corresponding cluster size ranges reported to date. Detailed bonding analyses indicate that the icosahedral B122-, CB11-, and C2B10 cores in these core-shell structures possess the superatomic electronic configuration of 1S21P61D101F8, rendering spherical aromaticity and extra stability to the systems. Such superatomic icosahedral-CnB12-n stuffed borafullerenes and borospherenes with spherical aromaticity may serve as embryos to form bulk boron allotropes and their carbon-boron binary counterparts in bottom-up approaches.