Quantitative analysis of thin-film conductivity by scanning microwave microscope

We propose a novel method for high-throughput quantitative analysis of thin-film conductivity σ by using a scanning microwave microscope (SμM). We demonstrated that composition spread thin films of Ti_1-xNb_xO₂ can be utilized as a standard reference in a wide σ range. The shift in Q-value measured by SμM along the composition-spread axis showed a single peak, which moved to the lower x side with film thickness. This behavior was confirmed by electrical field simulation using the finite element method.     

Transport property characterization of sparse CNT networks via AFM images

A simulation method for correlating the resistivity and resistance of sparse carbon nanotube (CNT) networks via atomic force microscopy images was proposed. For the demonstration, resistance values simulated by this method were compared with values obtained by directory measuring the resistance of sparse CNT networks. Results were also compared with those obtained by a thin-film approximation in which CNT networks are approximated as thin rectangles. Simulated resistance values were closer to the experimental values of the same samples than those estimated on the basis of the thin-film approximation. The use of atomic force microscopy (AFM) images enabled the implementation of inhomogeneity to numerical models, as well as one-to-one comparison between real samples and numerical models.     

Raman sum rule and the relation to the infrared sum rule in La2-xSrxCuO4

Electronic Raman scattering has no sum rule in no and weak correlation, but the existence of sum rule has been proposed in strong correlation. The present Raman scattering disclosed that the first moment of the Raman susceptibility is proportional to the generalized moment of the optical conductivity in the metallic phase. The present experiment disclosed that a large amount of electronic states are incoherent states. The incoherent states are the relevant states for the superconductivity, because the gap opens in the incoherent states as well as the coherent states.     

Intermediates of halogen addition to phenylethynes and protonation of phenylethynyl halides. Open halovinyl cations, bridged halonium, or phenyl-bridged ions: a substituent effect study by DFT and GIAO-DFT

Formation of alpha-phenyl-beta-halovinyl cation, beta-phenyl-alpha-halovinyl cation, as well as the halogen-bridged and the spirocyclic phenyl-bridged cations as intermediates of protonation of phenylethynyl halides or by halogen addition to phenylethynes was evaluated by DFT at B3LYP/6-31+G(d) and, for comparison in representative cases, by B3LYP/6-311++G(d,p). Relative stabilities of the resulting minima were gauged as a function of substituents on the phenyl group with p-OH, p-OMe, p-H, p-CF3, p-CN, and p-NO2 and with p-OMeH+, p-NO2H+, and p-N2+. In the majority of cases, the alpha-aryl-beta-halovinyl cations were identified as the most likely intermediates, irrespective of X and for most R groups. For R = p-N2+ (with X = Br and Cl), R = CNH+ (with X = Cl), and R = MeOH+ (with X = Br), the corresponding beta-aryl-alpha-halovinyl cations become more stable than alpha-aryl-beta-halovinyl cations (but in most cases with a relatively small stability difference). Whereas competitive formation of the spirocyclic aryl bridged cations via this route appears remote, with R = N2+ and R = NO2H+ as substituents (with X = Br), cyclic halonium ions could intervene, since their relative stabilities are within approximately 4 kcal/mol of the lowest energy vinyl cations. Geometrical features, GIAO NMR chemical shifts, and NPA-derived charges were used to gain insight into the structural/electronic features in the resulting mono and dications. The study provides a basis for stable ion and solvolytic/kinetic studies on a series of substituted phenylethynyl halides that are being synthesized.     

Dispersion and separation of small-diameter single-walled carbon nanotubes

The dispersion of small-diameter single-walled carbon nanotubes (SWNTs) produced by the CoMoCAT method in tetrahydrofuran (THF) with the use of amine was studied. The absorption, photoluminescence, and Raman spectroscopies showed that the dispersion and centrifugation process leads to an effective separation of metallic SWNTs from semiconducting SWNTs. Since this method is simple and convenient, it is highly applicable to an industrial utilization for widespread applications of SWNTs.     

Transannular pi-pi interactions in janusenes and in related rigid systems with cofacial aromatic rings; gauging aromaticity in the hydrocarbons and in model carbocations; a DFT study

The utility of NICS (nuclear independent chemical shift) as a probe for detecting/sensing variation in aromaticity due to transannular pi-pi interactions in janusene , a [3.3]orthocyclophane having two cofacial benzene rings within van der Waals distance, its tetrafluoro- and octafluoro-derivatives and , and in tropiliojanusene was studied by DFT at the B3LYP/6-31G(d) level. The related hydrocarbons and with a buried double-bond and their carbocations were also included in this study. Whereas NICS(0) and NICS(1) are rather insensitive to transannular interactions, computed NICS(1)(zz), values are larger and more negative for both pi-decks in the interannular space and this is consistent with increased transannular pi-pi interactions in the cofacial rings, previously shown in these systems via spectroscopic studies (UV and NMR), and by electrophilic chemistry. Transannular effects in , , and were also probed by examining the forms of HOMO-LUMOs. Attempts to measure donor-accepter interactions between electron rich/electron poor cofacial decks via NICS (1)(zz) through substituent effects proved unsuccessful, resulting in only very small changes. Protonation of the double-bond buried in between the two pi-decks in and results in internally pi-stabilized carbocations that exhibit more negative NICS(1) and NICS(1)(zz) values in the interannular space. GIAO NMR data were computed for the neutral hydrocarbons and their derived carbocations, as a guiding tool for planned experimental studies.     

Temperature-modulated differential scanning calorimetry of reversible and irreversible first-order transitions

Temperature-modulated differential scanning calorimetry of first-order transitions has led to many new observations. Some of these involve non-linear processes or deal with transformations of practically instantaneous response. The latter may cause serious lags within the calorimeter due to limited thermal conductivity of the sample and the instrument. In both cases the “reversing heat capacity” or a “complex heat capacity” is not a precise representation of the transition since both are computed from abbreviated Fourier transforms, limited to the evaluation of the first harmonic component. One has in these cases to work in the time-domain with the raw output. But even from these analyses in the time-domain many interesting new insights about the transition and the calorimeter performance can be generated.     

Reaction of 3-amino-5,6-dimethyl-1,2,4-triazine with electrophiles

The title compound was reacted with four types of electrophiles and the respective reaction sites were investigated. The reaction with aryl isocyanates in the conventional way yielded the corresponding ureas. In the presence of triethylamine, the 3-amino group was diacylated with acyl chlorides. On the other hand, in the cases with arylsulfonyl chlorides and p-nitrobenzaldehyde under similar conditions, the methyl group at 5-position was preferentially attacked to give arylsulfonylmethyl and p-nitrostyryl derivatives, respectively.