Photochemical hole burning in macromolecular complexes

Photochemical hole burning (PHB) of free-base porphyrins in host polymers as a site-selective spectroscopy reveals the existence of vibronic structure in a porphyrin Q-band peak and low-energy excitation modes of host polymers. A new mechanism of photon-gated PHB by two-color sensitization of photoreactive polymers with a zinc porphyrin is also presented.     

BaF（Cl,Br）：Sm^2＋的光谱烧孔与光激励发光过程

Ｘ射线辐照前后，在ＢａＦ（Ｃｌ，Ｂｒ）：Ｓｍ＾２＋中以５６０ｎｍ的Ｎｄ：ＹＡＧ脉冲光在液氮温度下进行了双光子烧孔实验和光激励发光实验，结果表明，Ｓｍ＾２＋掺杂的碱土金属氟卤化物光谱烧孔过程中伴随着光激励发光过程，这一过程直接影响光谱烧孔过程的进行。     

Studies on Photon-gated Persistent Spectral Holeburning of Porphyrin Compounds as Optical Storage Materials

The present paper reports persistent and photon-gated persistent spectral holeburning films made up of zinc-tetrasulfobenzoporphyrin(ZnTPPS_t) with polyvinyl alcohol(PVA) host and made up of zinc-tetraphenylbenzoporphyrin(ZnTPBP,donor), p-hydroxybenzaldhytle(PHBA, acceptor)and polymethylmethacrylate (PMMA, host). The experimental results show that ZnTPPS_t, and ZnTPBP have the character of single-pholon (one-tolor) and photon-gated (two-color) spectral holeburning,respectively.     

Coherent Surface Plasmon Hole Burning via Spontaneously Generated Coherence

Surface plasmon (SP)—induced spectral hole burning (SHB) at the silver-dielectric interface is investigated theoretically. We notice a typical lamb dip at a selective frequency, which abruptly reduces the absorption spectrum of the surface plasmons polaritons (SPP). Introducing the spontaneous generated coherence (SGC) in the atomic medium, the slope of dispersion becomes normal. Additionally, slow SPP propagation is also noticed at the interface. The spectral hole burning dip is enhanced with the SGC effect and can be modified and controlled with the frequency and intensity of the driving fields. The SPP propagation length at the hole-burning region is greatly enhanced under the effect of SGC. A propagation length of the order of 600 µm is achieved for the modes, which is a remarkable result. The enhancement of plasmon hole burning under SGC will find significant applications in sensing technology, optical communication, optical tweezers and nano-photonics.     

Photochemical hole burning by photoinduced electron transfer. Effects of sacrificially consumable molecules

Photochemical hole burning by photoinduced electron transfer was studied with emphasis on the effects of sacrificially consumable molecules. A backward electron-transfer process reduces the total efficiency of electron transfer. In order to enhance the effective electron transfer and to suppress the backward electron transfer, sacrificially consumable molecules were introduced to the donor—acceptor electron-transfer systems. In the presence of sacrificially consumable molecules, the efficiency of hole formation increased remarkably. The two-color enhancement of hole formation was also observed for a suitable acceptor.     

Influence of temperature and pressure on shape and shift of impurity optical bands in polymer glasses

The shape, broadening, and shift of optical absorption spectra of molecular impurity centers in polymer glasses are considered in terms of inhomogeneous energy distributions and coupling of electronic transitions to vibrations. Persistent spectral hole burning was applied for frequency-selective probing of zero-phonon lines. The shift and broadening of spectral holes were studied between 5 and 50 K and by applying a hydrostatic He gas pressure up to 200 bar. Broadband absorption spectra were recorded between 5 and 300 K in poly(methyl methacrylate) and polyethylene. In addition to "normal" thermal broadening, due to the first- and second-order electron phonon coupling, several narrowing components were predicted on the basis of frequency dependent hole behavior. Thermal expansion of the matrix and the relaxation of local strains, previously accumulated on cooling below the glass temperature can lead to shrinking of the inhomogeneous width. A Voigt treatment of absorption band shapes reveals that the Gaussian component can indeed suffer remarkable narrowing. Inhomogeneous band shapes and the frequency-dependent thermal and baric line shifts were rationalized with the aid of a pair of two-body Lennard-Jones potentials. The shift of potential well minima is a crucial factor influencing solvent shifts, inhomogeneous band shapes, pressure shift coefficients, and quadratic electron phonon coupling constants.     

Persistent spectral hole‐burning study on dendrimer porphyrins

We report the first results of persistent spectral hole burning of dendrimer porphyrins having three‐, four‐, or five‐layered aryl ether dendritic arrays. We evaluate structural relaxations of dendrimer framework around the porphyrin core at low temperatures. A large environmental change around the porphyrin core, as evaluated from the hole area, was suppressed in dendrimer porphyrins of higher generation numbers, whereas a small environmental change, as evaluated from hole width, showed no dependence on the number of generations. The dendrimer porphyrins showed sharp holes at 20 K, suggesting a long dephasing time and the suppression of spontaneous spectral diffusion. The results of dendrimer‐embedded polymer sample indicated that the structural relaxation of polymer chain outside the dendrimer does not have an influence on the resonant frequency of the porphyrin core. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 210–215, 2002     

Room Temperature Persistent Spectral Hole-Burning in Sol-Gel-Derived Glasses Doped with Eu3+ Ions

Persistent spectral hole burning was investigated for the Eu³⁺ ions-doped glasses prepared by a sol-gel method. For the glasses containing OH bonds, persistent spectral hole is burned by the laser-induced rearrangement of the OH bonds surrounding the Eu³⁺ ions, which is thermally unstable to erase up to 200 K. On the other hand, the Eu³⁺-doped Al₂O₃-SiO₂ glasses which are heated under H₂ gas or irradiated with X-ray exhibit room temperature PSHB. The depth of the burnt hole increases as the Al₂O₃ content increases. The hole-formation could be explained by a model of the excitation of the Eu³⁺ ions and subsequent electron transfer with the excited [Eu³⁺]^– or oxygen-defect centers in the Al—O bonds. The burnt holes are more stable compared with those burned by the rearrangement of the OH bonds.     

Low‐temperature relaxation of polymers around doped dyes studied by persistent spectral hole burning

Persistent spectral hole burning spectroscopy is applied to evaluate the low‐temperature relaxation around the dye molecules doped in several types of polymers. The doped dye is tetraphenylporphine, and the measured polymers are vinyl polymers and main chain aromatic polymers. The changes of microscopic environments around the dye are evaluated from the changes in the hole profiles during temperature cycling experiments. The relaxation behavior of the polymers is discussed in relation to their chemical structures. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 585–592, 1999     

光谱烧孔材料苯并卟啉锌配合物的电化学及现场光谱电化学特性

在CH₂Cl₂、THF及DMSO中研究了系列光谱烧孔材料苯并卟啉锌配合物的电化学及光谱电化学特性,给出不同结构的苯并卟啉锌配合物的氧化还原电位及相应氧化还原态的光谱,结合光谱数据和氢化还原电位数值估算了与光化学光谱烧孔过程密切相关的分子激发态氧化还原电位。     

含碘系列电荷转移复合物的热分解温度对烧孔阈值电压的影响

合成了5种含碘的电荷转移复合物,对其热化学烧孔性能进行了研究,在它们的单晶上成功写入了信息点阵.通过热重分析获得了5种材料的热分解温度,并测量了它们的烧孔阈值电压.结果表明,材料的热分解温度对烧孔阈值电压有明显影响.理论分析表明,阈值电压对热分解温度的依赖关系反映了活化能对热化学烧孔反应速度的影响.     

Investigation of spectral diffusion in ribonuclease by photolabeling of intrinsic aromatic amino acids

Spectral diffusion dynamics in ribonuclease A was observed via the broadening of photochemical holes burned into the absorption spectrum of intrinsic tyrosine residues. Unlike previous results based on hole burning of chromophores in the pockets of heme proteins, where spectral diffusion develops according to a power law in time, the dynamics in ribonuclease follow a logarithmic law. The results suggest that the experiment preferentially labels the tyrosines located on the surface of the protein where the two-level system dynamics of the glass host matrix exert a strong influence.     

Thermochemical hole burning on a series of N-substituted morpholinium 7,7,8,8-tetracyanoquinodimethane charge-transfer complexes for data storage

We demonstrate here the thermochemical hole burning (THB) effect on a series of N-substituted morpholinium 7,7,8,8-tetracyanoquinodimethane charge-transfer (C-T) complexes for ultra-high-density data storage. A correlation between the decomposition temperature of the charge-transfer complex and the threshold voltage of hole burning was observed: the higher the decomposition temperature, the larger the writing threshold value, suggesting the possibility of molecular design for optimizing the hole burning performance. The macroscopic decomposition properties of these charge-transfer complexes were studied by thermal gravimetry combined with mass spectrometry. Theoretical estimation of the temperature rise induced by scanning tunneling microscopy current heating was also conducted, which indicated that the maximum temperature certainly exceeds the decomposition temperatures of these C-T complexes. These observations are consistent with the thermochemical hole burning mechanism.     

Prospects of Sol-Gel Process for Spectral Hole-Burning Glasses

Persistent spectral hole burning was studied in Eu³⁺ ions-doped Al₂O₃-SiO₂ glass prepared by a sol-gel method. The gel synthesized by the hydrolysis of Si- and Al-alkoxides and EuCl₃·6H₂O was heated in air and hydrogen gas atmospheres. For the glass heated in air to contain OH bonds, the hole was formed by the photoinduced rearrangement of the OH bonds surrounding the Eu³⁺ ions, and was thermally refilled and erased above 200 K. On the other hand, the glass heated in hydrogen gas showed the hole spectrum above 200 K. It was found that the hole depth was independent of the temperature and was 7% of the total intensity at room temperature. The proposed mechanism was the electron transfer between the Eu³⁺ ions and the defect centers formed in glass matrix.     

Four-color hole burning spectra of phenol/ammonia 1:3 and 1:4 clusters

The hole burning spectra of phenol/ammonia (1:3 and 1:4) clusters were measured by a newly developed four-color (UV-near-IR-UV-UV) hole burning spectroscopy, which is a kind of population labeling spectroscopy. From the hole burning spectra, it was found that single species is observed in an n = 3 cluster, while three isomers are observed simultaneously for n = 4. A possibility was suggested that the reaction efficiency of the hydrogen transfer from the electronically excited phenol/ammonia clusters, which was measured by a comparison with the action spectra of the corresponding cluster, depends on the initial vibronic levels.     

光子存储原理与光致变色材料

光子存储是信息科学中的一个前沿课题。本文主要包括以下内容: 光子存储的4种方式; 光子烧孔、电子捕获、光折变和光致变色存储的原理和材料; 双光子三维光存储原理和材料; 可能的发展方向。     

Heterogeneous thermal excitation and relaxation in supercooled liquids

We investigate a phenomenological model which rationalizes the effects of dielectric hole burning on the basis of heterogeneous dielectric and specific heat relaxation in supercooled liquids. The quantitative agreement between model predictions and dielectric hole-burning observations is lost if the assumption of correlated dielectric and thermal relaxation times is removed from the model. This suggests that dynamically distinct domains in real liquids are associated with a time constant which characterizes both the structural and thermal relaxation behaviors. The calculations demonstrate that the observed burn-induced modifications reflect the spectral selectivity and persistence time of the fictive temperatures within these domains, and that 100 or more cycles of the sinusoidal burn field can be required to saturate the heat accumulated in the slow degrees of freedom. It is also shown that the recovery of dielectric holes is entirely accounted for by the model, and that the persistence times do not provide direct insight into rate exchange processes. Additionally, the model predicts that the heating effects considered here are a significant source of nonlinear dielectric behavior, even in the absence of deliberate frequency selective hole burning.     

High-resolution optical spectroscopy of polymers: Molecular potentials and internal fields

Photochemical hole burning is a spectroscopic method which creates, via laser irradiation at low temperatures, narrow persistent dips in the inhomogeneous absorption bands of solids which are doped with appropriate dye molecules. Especially in amorphous samples, the spectral width of these dips can be several orders of magnitude smaller than that of the total inhomogeneous bands. This does not only provide an enormous increase in spectral resolution, but in addition it allows to select very small subsets of absorbers in the sample with accidentally degenerate transition frequencies. It can be shown that by applying external fields, material parameters and molecular potentials can be probed.     

Spectral hole-burning and holography

A review of recent work in which persistent spectral holes have been burnt as laser induced gratings (plane wave holograms) in the inhomogeneously broadened absorption bands of dye doped polymers is presented. The holographic detection technique is compared to the transmission technique and it is shown that a comparison of transmission and holographic hole widths leads to a direct measurement of homogeneous linewidth. Interference between spectrally adjacent gratings is dependent on the relative phase selected during burning. This consideration is important in the analysis of interference between spectrally adjacent gratings which are split through the application of an external electric field. Finally, the influence of the reconstruction symmetry is described.     

Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: an experimental and theoretical comparison

In this study we focus on the differences and analogies of two experimental implementations of two-dimensional infrared (2D-IR) spectroscopy: double-resonance or dynamic hole burning 2D-IR spectroscopy and pulsed Fourier transform or heterodyne detected photon echo spectroscopy. A comparison is done theoretically as well as experimentally by contrasting data obtained from both methods. As an example we have studied the strongly coupled asymmetric and symmetric carbonyl stretching vibrations of dicarbonylacetylacetonato rhodium dissolved in hexane. Both methods yield the same peaks in a 2D-IR spectrum. Within certain approximations we derive an analytic expression which shows that the 2D-IR spectra are broadened in one frequency dimension in the double-resonance experiment by convolution with the pump pulse spectral width, while the spectral resolution in the other frequency direction is the same in both cases.