Spectral Hole Burning in Hyperquenched Glassy Films and Biomolecular Gels: Science and Applications

摘要 9630781 小 建议的研究的灵感主要是由一个通用的热喷雾为基础的hyperquenching设备的发展，可再生的玻璃化的液体和它的成功应用，与非光化学烧孔和其他光谱，铝酞菁四磺酸盐（APT）在hyperquenched玻璃状水膜（HGW）。 在给定的温度下，不同的历史准备（沉积温度，退火程序）的研究薄膜的能力开辟了道路，为进一步详细研究的热力学连续性/动力学访问之间的不同状态的玻璃，无序诱导和其他机制的光学退相，电子-声子耦合和非光化学烧孔的机械方面。为此，磺化铝酞菁和试卤灵超淬膜的乙醇和甲醇和花青染料HITCI在乙二醇玻璃将被使用。这些数据将与理论一起用于测试烧孔和光子回波技术的结合是理解液体中光学相干损失的一种有前途的方法。提出了一种与压力相关（5 MPa）烧孔兼容的新型超猝灭装置的结构。它将被用来确定，例如，相对压缩率（5 K）的未退火和退火的HGW膜（APT作为发色团）。这是重要的，因为负责在低温下失相的本征二能级系统（TLSint）的密度在未退火的膜中比在退火的膜中高5倍。因此，可以检验TLSint与玻璃的过量自由体积密切相关的假设。根据目前的NSF赠款完成的工作也表明，在HGW中APT在低温和高温（-77 K）下的烧孔性能明显上级其他分子无定形系统。主要研究者建议 研究高水含量蛋白质凝胶（例如“Jello”）中的APT，其易于制备和高光学质量使其对于时域光学存储器/处理应用具有吸引力。目标是在77 K下实现600的频率存储密度，比缓冲HGW中的APT高四倍。APT在HGW的其他研究提出，目的是了解与异常有效的烧孔在低温和高温下的氢键开关和测试预测的APT/HGW（氘）的光存储器对破坏性读出由于烧孔和光诱导的孔填充的显着弹性。最后，红外烧孔实验与退火和未退火的HGW薄膜将进行，以确定从不均匀的加宽和振动激子耦合的基础结构的OH伸缩带的贡献。对这种结构的理解是一个令人着迷的长期感兴趣的问题，其解决方案与液态水的结构和分子间力有关。 无序及其对构型弛豫、能量和电荷传输、光谱跃迁动力学和复杂固体（如玻璃、聚合物和蛋白质）中的其他性质的影响是物理学、生物物理学和化学界的热门话题。这是可以理解的，因为理解受结构性无序强烈影响的物理和生物现象既重要又非常具有挑战性。此外，这种研究已经并将继续揭示新的物理和化学。该项目涉及分子玻璃中的构型弛豫和动力学，以及开发用于光学存储/处理和其他应用的新型高效、高温持久光谱烧孔材料。这些和其他项目旨在提供有关液体和玻璃中光学相干损失与高温下光学存储器破坏性读出之间关系的见解。

Abstract 9630781 Small The proposed studies are inspired mainly by the development of a versatile thermospray based-hyperquenching apparatus for reproducible vitrification of liquids and its successful application, with nonphotochemical hole burning and other spectroscopies, to Al-phthalocyanine tetrasulphonate (APT) in hyperquenched glassy films of water (HGW). The ability to study films at a given temperature with different histories of preparation (deposition temperature, annealing procedure) opens the way for further detailed studies of thermodynamic continuity / kinetic accessibility between different states of a glass, disorder-induced and other mechanisms for optical dephasing, electron-phonon coupling and mechanistic aspects of nonphotochemical hole burning. To this end, sulphonated Al-phthalocyanines and resorufin in hyperquenched films of ethanol and methanol and the cyanine dye HITCI in ethylene glycol glasses will be used. The data will be used with theory to test the suggestion that the marriage of hole burning and photon echo techniques is a promising approach to understanding optical coherence loss in liquids. Construction of a novel hyperquenching apparatus compatible with pressure dependent ( 5 MPa) hole burning is proposed. It would be used to determine, for example, the relative compressibilities (5 K) of unannealed and annealed HGW films (APT as the chromophore). This is important because the density of intrinsic two level systems (TLSint), responsible for dephasing at low temperatures, is a factor of 5x higher in unannealed than in annealed films. Thus, it will be possible to test the hypothesis that TLSint are intimately associated with the excess free volume of glasses. Work completed under the current NSF grant has also shown that the hole burning properties of APT in HGW at low and high temperatures (- 77 K) are significantly superior to those of other molecular amorphous systems. The Principal Investigator proposes to study APT in high water content protein gels (e.g. "Jello") whose ease of preparation and high optical quality make them attractive for time domain optical memory/processing applications. The goal is to achieve a frequency storage density of 600 at 77 K, a factor of four higher than that for APT in buffered HGW. Additional studies of APT in HGW are proposed, the objectives being to understand the hydrogen-bond switching associated with the exceptionally efficient hole burning at both low and high temperatures and to test predictions of a notable resilience of APT/HGW (deuterated)'s optical memory against destructive readout due to hole burning and light-induced hole filling. Finally, infra-red hole burning experiments with annealed and unannealed HGW films will be performed in order to determine the contributions from inhomogeneous broadening and vibrational excitonic coupling to the underlying structure of the OH stretching band. The understanding of this structure is a fascinating problem of longstanding interest, one whose solution bears on the structure and intermolecular forces of liquid water. %%% Disorder and its effects on configurational relaxation, energy and charge transport, the dynamics of spectroscopic transitions and other properties in complex solids, such as glasses, polymers and proteins, are subjects of intense interest in the physics, biophysics and chemistry communities. This is understandable since to understand physical and biological phenomena which are strongly influenced by structural disorder is both important and very challenging. Furthermore, such research has and will continue to reveal new physics and chemistry. This project is concerned with configurational relaxation and dynamics in molecular glasses and the development of a new class of efficient, high temperature persistent spectral hole burning materials for optical memory/processing and other applications. These and other projects are designed to provide insights on the relationship between optical coherence loss in liquid and glasses, and destructive readout of optical memory at high temperature.