Synthesis of Nitrogen‐Doped ZigZag‐Edge Peripheries: Dibenzo‐9a‐azaphenalene as Repeating Unit

A bottom‐up approach toward stable and monodisperse segments of graphenes with a nitrogen‐doped zigzag edge is introduced. Exemplified by the so far unprecedented dibenzo‐9a‐azaphenalene (DBAPhen) as the core unit, a versatile synthetic concept is introduced that leads to nitrogen‐doped zigzag nanographenes and graphene nanoribbons.     

Luminol chemiluminescense reaction: a new method for monitoring nitric oxide in vivo

A new method employing a combination of microdialysis sampling and chemiluminescence (CL) detection was developed to monitor nitric oxide (NO) in vivo. A special probe was designed with an interference-free membrane to achieve very high selectivity for NO. High sensitivity was achieved by optimizing the working system and improving the NO sampling time. This system was used in vivo to monitor blood and brain tissue in rats and rabbits. The system is sensitive enough to detect variations of NO formation under different physiological states. The linear valid range of NO determination is 5 nM to 1 μM, with a 3σ detection limit of 1 nM; real NO concentrations in test animals used in this work were found to be in the range of 1-5 nM or even less. Finally, the effects of body temperature, NO donors, Viagra, NO activators, NO cofactors and NO interference (such as O₂) were investigated carefully in different physiological situations.     

c(2×2) water-hydroxyl layer on Cu(110): a wetting layer stabilized by Bjerrum defects

Understanding the composition and stability of mixed water-hydroxyl layers is a key step in describing wetting and how surfaces respond to redox processes. Here we show that, instead of forming a complete hydrogen bonding network, structures containing an excess of water over hydroxyl are stabilized on Cu(110) by forming a distorted hexagonal network of water-hydroxyl trimers containing Bjerrum defects. This arrangement maximizes the number of strong bonds formed by water donation to OH and provides uncoordinated OH groups able to hydrogen bond multilayer water and nucleate growth.     

Quantum nuclear effects on the location of hydrogen above and below the palladium (100) surface

We report ab initio path integral molecular dynamics simulations of hydrogen and deuterium adsorbed on and absorbed in the Pd(100) surface at 100 K. Significant quantum nuclear effects are found by comparing with conventional ab initio molecular dynamics simulations with classical nuclei. For on-surface adsorption, hydrogen resides higher above the surface when quantum nuclear effects are included, an effect which brings the computed height into better agreement with experimental measurements. For sub-surface absorption, the classical and quantum simulations differ in an even more significant manner: the classically stable subsurface tetrahedral position is unstable when quantum nuclear effects are accounted for. This study provides insight that aids in the interpretation of experimental results and, more generally, underscores that despite the computational cost ab initio path integral molecular dynamics simulations of surface and subsurface adsorption are now feasible.     

Raman Scattering Study on Vibrational Modes and Structure of Lanthanum Tellurite Glasses

Raman spectra of xLa₂O₃-(1-x)的TeO₂(x=0、0.05、0.10、0.15、0.20和0.25) lanthanum tellurite glasses were measured and analyzed over the entire glass-forming region in an effort to quantitatively follow the structural changes caused by lanthanum oxide variation. For the first time, systematic intensity measurements have been performed to elucidate the composition induced structural changes in the high-frequency stretching vibration region and a possible mechanism was proposed. The network structure of the glasses is formed by mixing TeO₄ trigonal bipyramid and TeO₃ trigonal pyramid units. The change of the lanthanum oxide content results in conversion of the TeO₄ units to TeO₃ units with a varying number of non-bridging oxygen atoms. Analysis of the Raman band contours in terms of vibrations due to different oxygen bridged trigonal bipyramid and trigonal pyramid tellurite structural units, allowed to calculate the relative amounts of the species involved in the structural changes with composition. The fraction of the terminal oxygen atoms has been estimated from the Raman intensities with the aid of a structural model concerning the structure of tellurite network systems. The simulation of the experimental density of lanthanum tellurite glasses with modifier content up to 25% revealed that the short range order building units assumed here are sufficient to account for the overall structure in these glasses.     

Measurement of the electronic transition dipole moment by Autler-Townes splitting: Comparison of three- and four-level excitation schemes for the Na2 A 1Sigma(u)+ - X 1Sigma(g)+ system

We present a fundamentally new approach for measuring the transition dipole moment of molecular transitions, which combines the benefits of quantum interference effects, such as the Autler-Townes splitting, with the familiar R-centroid approximation. This method is superior to other experimental methods for determining the absolute value of the R-dependent electronic transition dipole moment function mu(e)(R), since it requires only an accurate measurement of the coupling laser electric field amplitude and the determination of the Rabi frequency from an Autler-Townes split fluorescence spectral line. We illustrate this method by measuring the transition dipole moment matrix element for the Na2 A 1Sigma(u)+ (v' = 25, J' = 20e)-X 1Sigma(g)+ (v" = 38, J" = 21e) rovibronic transition and compare our experimental results with our ab initio calculations. We have compared the three-level (cascade) and four-level (extended Lambda) excitation schemes and found that the latter is preferable in this case for two reasons. First, this excitation scheme takes advantage of the fact that the coupling field lower level is outside the thermal population range. As a result vibrational levels with larger wave function amplitudes at the outer turning point of vibration lead to larger transition dipole moment matrix elements and Rabi frequencies than those accessible from the equilibrium internuclear distance of the thermal population distribution. Second, the coupling laser can be "tuned" to different rovibronic transitions in order to determine the internuclear distance dependence of the electronic transition dipole moment function in the region of the R-centroid of each coupling laser transition. Thus the internuclear distance dependence of the transition moment function mu(e)(R) can be determined at several very different values of the R centroid. The measured transition dipole moment matrix element for the Na2 A 1Sigma(u)+ (v' = 25, J' = 20e)-X 1Sigma(g)+ (v" = 38, J" = 21e) transition is 5.5+/-0.2 D compared to our ab initio value of 5.9 D. By using the R-centroid approximation for this transition the corresponding experimental electronic transition dipole moment is 9.72 D at Rc = 4.81 A, in good agreement with our ab initio value of 10.55 D.     

"Textbook" adsorption at "nontextbook" adsorption sites: halogen atoms on alkali halide surfaces

Density-functional theory and second order M?ller-Plesset perturbation theory calculations indicate that halogen atoms bond preferentially to halide substrate atoms on a series of alkali halide surfaces, rather than to the alkali atoms as might be anticipated. An analysis of the electronic structures in each system reveals that this novel adsorption mode is stabilized by the formation of textbook two-center three-electron covalent bonds. The implications of these findings to, for example, nanostructure crystal growth, are briefly discussed.     

Insight into D6h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single‐Ion Magnets

Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph₃SiO^? (Ph₃SiO^?=anion of triphenylsilanol) and the 2,4‐di‐^tBu‐PhO^? (2,4‐di‐^tBu‐PhO^?=anion of 2,4‐di‐tertbutylphenol) ligands combined with the weak equatorial field of the ligand L^N6 , leads to [Dy^III(L^N6)(2,4‐di‐^tBu‐PhO)₂](PF₆) ( 1 ), [Dy^III(L^N6)(Ph₃SiO)₂](PF₆) ( 2 ) and [Dy^III(L^N6)(Ph₃SiO)₂](BPh₄) ( 3 ) hexagonal bipyramidal dysprosium(III) single‐molecule magnets (SMMs) with high anisotropy barriers of U_eff=973 K for 1 , U_eff=1080 K for 2 and U_eff=1124 K for 3 under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher‐order symmetry SMMs.     

Correlating changes in structure and dynamical properties in LnX<Subscript>3</Subscript> (Ln = Y,Ho, Dy,Gd, Nd,La and X = Cl,Br) ionic melts

Raman spectroscopy was used to probe the vibrational dynamics of LnX₃ molten salts for a variety of lanthanides (Ln = La, Nd, Gd, Dy, Ho, Y) and halides (X = Br, Cl). Analysis of the line profiles has been performed by employing a time-correlation function with an analytical counterpart in the frequency domain, which permits fitting of specific vibrational features in an effort to elucidate the structure and obtain dynamical information in parallel. It is established using 2-D correlation methodology that all lanthanide halides exhibit similar structural properties and analogous vibrational relaxation and frequency modulation times. The structure of the lanthanide halide melts studied in this work is composed of distorted octahedra that constitute a loose network as reported before. The rigidity of the network is related to the splitting of the P ₁ and P ₂ bands, attributed to the ν ₁ (A_1g) and ν₅(F_2g ) fundamental octahedral modes, and increases with increasing distortion of the octahedra in the sequence La → Y and Cl → Br. A variety of picosecond dynamics models have been tested and found that only the Rothschild approach complies well with the experimental data assuming that the environmental modulation is described by a stretched exponential decay. The experimental results are discussed in terms of theoretical models providing insights in the inter-molecular coupling mechanisms.