Structural verification of a tetrahydrotetrazole compound

Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C₂₅H₃₀N₄O₄, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl₃). A tentative reaction pathway for its dissociation based on ¹H NMR spectral evidence is provided.     

A Six-Vertex Theorem for Bounding Normal Planar Curves

We prove that the number of vertices of a smooth normal planarcurve is at least 6, if it bounds a surface other than the disk.     

(2 + 1) Resonance enhanced multiphoton ionization of hydrogen chloride in a pulsed supersonic jet: Vacuum wavenumbers of rotational lines with detailed band analysis for excited electronic states of HCl

A comprehensive study of the excited electronic states of HCl is reported. Using resonance enhanced multiphoton ionization ((2 + 1) REMPI) and time-of-flight mass spectrometry (TOFMS) over 120 band systems are analyzed. Supersonic jet techniques are used to prepare rotationally cold species for laser spectroscopy in the 77 000 to 96 000 cm⁻¹ region. At least 50 new electronic states are characterized as well as several features only tentatively assigned previously. A long vibrational progression consisting of 29 vibrational levels of the deeply bound V¹Σ⁺(0⁺) valence/ion-pair state is studied. We also extend the identification and analysis to high vibrational levels of low-lying Rydberg states. The assignments of [²Π_i] Rydberg state complexes are evaluated in terms of spin-orbit coupling and united-atom calculations. In several band systems, the spectra exhibit anomalous rotational line intensities and broadened linewidths which are consistent with predissociation. Multiphoton ionization with mass spectrometry permits the investigation of isotope effects as well as the appearance of fragment species associated with repulsive potential curves.     

Spatial design matrices and associated quadratic forms: structure and properties

The paper provides significant simplifications and extensions of results obtained by Gorsich, Genton, and Strang (J. Multivariate Anal. 80 (2002) 138) on the structure of spatial design matrices. These are the matrices implicitly defined by quadratic forms that arise naturally in modelling intrinsically stationary and isotropic spatial processes. We give concise structural formulae for these matrices, and simple generating functions for them. The generating functions provide formulae for the cumulants of the quadratic forms of interest when the process is Gaussian, second-order stationary and isotropic. We use these to study the statistical properties of the associated quadratic forms, in particular those of the classical variogram estimator, under several assumptions about the actual variogram.     

Solution Regularity in Optimal Control via Subgradient Analysis of the Value Function

Lipschitz regularity for solutions to nonsmooth problems in the calculus of variations is considered, where we allow for extended-real-valued Lagrangians. Conditions for regularity are given in terms of subdifferentiability properties of the value function. In particular, it is shown that there exists a Lipschitz minimizer as long as the limiting subgradient of the value function is nonempty at the point in question. The results improve upon previous results in the literature, even in the case of finite Lagrangians.     

Random sequence multisets for synchronous code-divisionmultiple-access channels

The effect of using randomly selected sequence multisets for the uplink of a synchronous code-division multiple-access channel is considered. A tight lower bound on the expected value of the sum capacity over the ensemble of randomly selected sequence multisets is given. For large systems, the sum rate penalty for using randomly selected multisets is shown to be at most 1 nat and to vanish as the number of users becomes large, compared to the sequence length     

Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.     

Time-resolved electron transport studies on InGaAs/GaAs-QWIPs

Due to the short internal response time, quantum-well infrared photodetectors (QWIPs) are interesting for high-speed applications such as heterodyne spectroscopy or laser pulse monitoring. We studied the photocurrent transients of InGaAs/GaAs-QWIPs after irradiation with infrared laser pulses of 250 fs duration. The excitation wavelength of about 9 μm matches the peak wavelength of the QWIP structure. The photocurrent transient consists of two different dynamical components, representing the fast photoionization in the quantum-wells and the slow injection current that compensates the remaining space charge. The investigations of the different components as a function of temperature and bias voltage were performed on a nanosecond time-scale. The experimental separation of the two photocurrent contributions allows us to determine the photoconductive gain. The Fourier transform of the photocurrent transient was compared with other experimental methods including heterodyne detection and microwave rectification. The quantitative agreement between these different measurement techniques is excellent.     

Modules of piecewise polynomials and their freeness

Partially supported by NSF Grant DMS-9004123 and ARO through MSI Cornell (DAAG 29-85-C-0018)