Large Enhancement of the Single-Molecular Conductance of a Molecular Wire through a Radical Substituent

The single-molecular conductance between two π-conjugated wires with and without a radical substituent has been compared. Specifically, methyl- and iminonitroxide-substituted 4-(biphenyl-4-yl)pyridine wires bound onto a porphyrin template were subjected to scanning tunneling microscopy (STM) apparent-height measurement at the interface between highly oriented pyrolytic graphite (HOPG) and octan-1-oic acid. Statistical analysis of the STM images revealed that the radical-substituted wire has 3.2±1.7-fold higher conductance than the methyl-substituted reference. Although density functional theory (DFT) calculation suggests that only 17 % of the SOMO is distributed on the wire moiety, the effect was significant. This study presents the potential of radical substituents to achieve high conductivity in molecular wires.     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Mechanistic Investigation and Conductance Modulation of a Metal-Molecule-Metal Junction via Extra Acid Addition

One important prerequisite for the fabrication of molecular functional device strongly relies on the understanding the conducting behaviors of the metal-molecule-metal junction that can respond to an external stimulus. The model Lewis basic molecule 4,4′-(pyridine-3,5-diyl)dibenzonitrile (DBP), which can react with Lewis acid and protic acid, was synthesized. Then, the molecular conducting behavior of DBP, DBP-B(C₆F₅)₃, and DBP-TfOH (DBP-B(C₆F₅)₃, and DBP-TfOH were produced by Lewis acid and protonic acid treatment of DBP) was researched and compared. Given that their identical physical paths for DBP, DBP-B(C₆F₅)₃, and DBP-TfOH to sustain charge transport, our results indicate that modifying the molecular electronic structure, even not directly changing the conductive physical backbone, can tune the charge transporting ability by nearly one order of magnitude. Furthermore, the addition of another Lewis base triethylamine (of stronger alkaline than DBP), to Lewis acid-base pair reverts the electrical properties back to that of a single DBP junction, that is constructive to propose a useful but simple strategy for the design and construction of reversible and controllable molecular device based on pyridine derived molecule.     

Accurate correction of arbitrary spin fermion quantum tunneling from non-stationary Kerr-de Sitter black hole based on corrected Lorentz dispersion relation

According to a corrected dispersion relation proposed in the study on the string theory and quantum gravity theory, the Rarita-Schwinger equation was precisely modified, which resulted in the Rarita-Schwinger-Hamilton-Jacobi equation. Using this equation, the characteristics of arbitrary spin fermion quantum tunneling radiation from non-stationary Kerr-de Sitter black holes were determined. A number of accurately corrected physical quantities, such as surface gravity, chemical potential, tunneling probability, and Hawking temperature, which describe the properties of black holes, were derived. This research has enriched the research methods and enabled increased precision in black hole physics research.     

TUNNEX: An easy-to-use wentzel-kramers-brillouin (WKB) implementation to compute tunneling half-lives

Tunneling in experiments (TUNNEX) is a free open-source program with an easy-to-use graphical user interface to simplify the process of Wentzel-Kramers-Brillouin (WKB) computations. TUNNEX aims at experimental chemists with basic knowledge of computational chemistry, and it offers the computation of tunneling half-lives, visualization of data, and exporting of graphs. It also provides a helper tool for executing the zero-point vibrational energy correction along the path. The program also enables computing high-level single points along the intrinsic reaction path. TUNNEX is available at https://github.com/prs-group/TUNNEX . As the WKB approximation usually overestimates tunneling half-lives, it can be used to screen tunneling processes before proceeding with elaborate kinetic experiments or higher-level tunneling computations such as instanton theory and small curvature tunneling approaches. © 2018 Wiley Periodicals, Inc.     

Imaging and tracking an electrostatic charge micro-domain by Kelvin force microscopy as evidence of water adsorption on mica surface

Muscovite mica is a widely accepted substrate for scanning probe microscopy (SPM) investigations. However, mica has intrinsic properties that alter samples and obstruct their analysis due to free charges build-up, ionic exchange and water adsorption taking place at the surface. In addition to interfacial phenomena, there is a growing interest in electrostatic charges on insulators as they are crucial in diverse applications. Despite the high demand for studies of this nature, experimental set-ups capable of resolving charge build-up at the micro-scale are still scarce and technically limited. Here, we report the imaging of surface charge dissipation on freshly cleaved mica by Kelvin-probe Force Microscopy (KPFM). A local electrostatic charge micro-domain was generated by friction between an atomic force microscope (AFM) tip and mica, and its decay was tracked by two-dimensional mapping using KPFM. We found time-dependent charge dissipation, which is attributed to the adsorption of water molecules on mica surface.     

塔河油田超埋深碳酸盐岩油藏基质的力学试验研究

碳酸盐岩油气藏在全球范围内分布广泛,其中30%以上为缝洞型碳酸盐岩油气藏。在我国缝洞型油藏占已探明的碳酸盐岩油藏储量的2/3,是今后增储的主要领域。为准确揭示碳酸盐岩油藏基质的力学特性,本文以塔河油田奥陶系油藏地层为研究背景,通过现场深孔钻井取样得到埋深达5300~6200m的碳酸盐岩油藏基质岩样,并通过力学试验首次获得超埋深碳酸盐岩油藏基质的弹模、泊松比、抗压强度、抗拉强度、粘聚力、内摩擦角等力学参数,借助电镜扫描试验揭示出超埋深碳酸盐岩的微细观破裂机制。该项研究成果可为分析碳酸盐岩油藏溶洞的垮塌破坏机理提供有效的试验参数。     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

Heavy-Atom Tunneling in Semibullvalenes: How Driving Force,Substituents, and Environment Influence the Tunneling Rates

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b .     

表/界面水的扫描探针技术研究进展

表面和界面水在自然界、人们的日常生活以及现代科技中无处不在.它在物理、化学、环境学、材料学、生物学、地质学等诸多基础学科和应用领域起到至关重要的作用.因此,表面和界面水的功能与特性的研究,是水基础科学的一项核心任务.然而,由于水分子之间氢键相互作用的复杂性,及其与水-固界面相互作用的竞争,使得表(界)面水对于局域环境的影响非常敏感,往往需要深入到分子层次研究其微观结构和动力学过程.近年来,新型扫描探针技术的发展使得人们可以在单分子甚至亚分子尺度上对表(界)面水展开细致的实空间研究.本文着重介绍几种代表性的扫描探针技术及其在表(界)面水体系中的应用,包括:超高真空扫描隧道显微术、单分子振动谱技术、电化学扫描隧道显微术和非接触式原子力显微术.此外,本文还将对表(界)面水扫描探针技术研究面临的挑战和未来发展方向进行了展望.