325 research outputs found

    Reorientational Dynamics and Solid-Phase Transformation of Ammonium Dicyanamide into Dicyandiamide

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    The reorientational dynamics of ammonium dicyanamide ND4[N(C≡N)2] and the kinetics as well as the mechanism of the solid-state isomerization reaction from ammonium dicyanamide into dicyandiamide (N≡C-N=C(NH2)2) was studied by means of 2H and 14N solid-state NMR spectroscopy in a temperature range between 38 and 390 K. Whereas in previous investigations the mechanism of the solid-state transformation was investigated by means of vibrational and magic angle spinning solid-state NMR spectroscopy as well as neutron diffraction, we here present a comprehensive 2H study of the ammonium ion dynamics prior to and during the course of the reaction, thereby highlighting possible cross correlations between dynamics and reactivity involving the ammonium ion. The ND4+ group was found to undergo thermally activated random jumps in a tetrahedral potential, which is increasingly distorted with increasing temperature, giving rise to an asymmetrically compressed or elongated tetrahedron with deviations from the tetrahedral angle of up to 6°. The correlation time follows an Arrhenius law with an activation energy of Ea = 25.8(2) kJ mol-1 and an attempt frequency of τ0-1 = 440(80) THz. The spin−lattice relaxation times were fitted according to a simple Bloembergen−Purcell−Pound type model with a T1 minimum of 4 ms at 230 K. Temperature-dependent librational amplitudes were extracted by line-shape simulations between 38 and 390 K and contrasted with those obtained by neutron diffraction, their values ranging between 5 and 28°. The onset and progress of the solid-phase transformation were followed in situ at temperatures above 372 K and could be classified as a strongly temperature-dependent, heterogeneous two-step reaction proceeding with rapid evolution of ammonia and comparatively slow subsequent reintegration into the solid. On the microscopic level, this correlates with a rapid proton transferpossibly triggered by a coupling between the ammonium ion dynamics and phonon modes on the terahertz time scaleand an essentially decoupled nucleophilic attack of ammonia at the nitrile carbon, giving rise to significantly differing time constants for the two processes

    Super Resolution of Wavelet-Encoded Images and Videos

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    In this dissertation, we address the multiframe super resolution reconstruction problem for wavelet-encoded images and videos. The goal of multiframe super resolution is to obtain one or more high resolution images by fusing a sequence of degraded or aliased low resolution images of the same scene. Since the low resolution images may be unaligned, a registration step is required before super resolution reconstruction. Therefore, we first explore in-band (i.e. in the wavelet-domain) image registration; then, investigate super resolution. Our motivation for analyzing the image registration and super resolution problems in the wavelet domain is the growing trend in wavelet-encoded imaging, and wavelet-encoding for image/video compression. Due to drawbacks of widely used discrete cosine transform in image and video compression, a considerable amount of literature is devoted to wavelet-based methods. However, since wavelets are shift-variant, existing methods cannot utilize wavelet subbands efficiently. In order to overcome this drawback, we establish and explore the direct relationship between the subbands under a translational shift, for image registration and super resolution. We then employ our devised in-band methodology, in a motion compensated video compression framework, to demonstrate the effective usage of wavelet subbands. Super resolution can also be used as a post-processing step in video compression in order to decrease the size of the video files to be compressed, with downsampling added as a pre-processing step. Therefore, we present a video compression scheme that utilizes super resolution to reconstruct the high frequency information lost during downsampling. In addition, super resolution is a crucial post-processing step for satellite imagery, due to the fact that it is hard to update imaging devices after a satellite is launched. Thus, we also demonstrate the usage of our devised methods in enhancing resolution of pansharpened multispectral images

    Differential correction methods in spacecraft attitude determination

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    Differential correction methods in spacecraft attitude determinatio
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