Terahertz Spectroscopy

太赫兹光谱学
  • 文章类型: Journal Article
    软纳米约束下的水具有与散装水根本不同的物理和化学性质;然而,限制系统和几何形状的多样性和特殊性掩盖了其任何潜在的普遍特征。这里,我们通过求助于脂质中间相作为理想的纳米约束系统来推进这一探索,允许在约束介质的拓扑和几何特性的系统变化下检查水的行为,而不改变界面的化学性质。通过结合太赫兹吸收光谱实验和分子动力学模拟,我们揭示了控制纳米承压水物理学的普遍定律的存在,概括了在不同水合和纳米约束拓扑水平下收集的数据。主曲线的存在证明了这种与几何形状无关的普遍性,该主曲线表征了模拟水的结构和动力学,作为与脂质-水界面距离的函数。根据我们的理论发现,我们预测了一个无参数定律,该定律描述了相对于系统结构尺寸的界面水量(即,晶格参数),在同一条曲线中捕获实验和数值结果,没有任何拟合。我们的结果提供了对软纳米约束下水的基本物理学的见解,并提供了一种实用的工具,用于根据结构实验数据准确估计非散装水的量。
    Water under soft nanoconfinement features physical and chemical properties fundamentally different from bulk water; yet, the multitude and specificity of confining systems and geometries mask any of its potentially universal traits. Here, we advance in this quest by resorting to lipidic mesophases as an ideal nanoconfinement system, allowing inspecting the behavior of water under systematic changes in the topological and geometrical properties of the confining medium, without altering the chemical nature of the interfaces. By combining Terahertz absorption spectroscopy experiments and molecular dynamics simulations, we unveil the presence of universal laws governing the physics of nanoconfined water, recapitulating the data collected at varying levels of hydration and nanoconfinement topologies. This geometry-independent universality is evidenced by the existence of master curves characterizing both the structure and dynamics of simulated water as a function of the distance from the lipid-water interface. Based on our theoretical findings, we predict a parameter-free law describing the amount of interfacial water against the structural dimension of the system (i.e., the lattice parameter), which captures both the experimental and numerical results within the same curve, without any fitting. Our results offer insight into the fundamental physics of water under soft nanoconfinement and provide a practical tool for accurately estimating the amount of nonbulk water based on structural experimental data.
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  • 文章类型: Journal Article
    基于石墨烯的太赫兹(THz)设备已经成为各种应用的有前途的平台,利用石墨烯独特的光电特性。这篇综述探讨了在太赫兹技术中利用石墨烯的最新进展,主要集中在THz分子传感和THz波调制两个方面。在分子传感中,石墨烯的环境敏感THz传输和发射特性用于实现分子吸附检测和生物分子传感。这种能力具有巨大的潜力,从检测农药到DNA的高灵敏度和选择性。在THz波调制中,对下一代无线通信系统至关重要,当门控时,石墨烯在吸收调制中显示出显著的潜力。新颖的器件结构,光谱系统,和超表面结构实现了增强的吸收和波调制。此外,空间相位调制和偏振操纵等技术已经被探索。从传感到通信,基于石墨烯的THz器件为未来的研究和开发提供了广泛的机会。最后,传感技术的进步不仅增强了生物分子分析,而且还有助于通过有效调制电磁波来优化石墨烯的通信性能。相反,通信策略的发展告知和增强感知能力,建立互惠互利的关系。
    Graphene-based terahertz (THz) devices have emerged as promising platforms for a variety of applications, leveraging graphene\'s unique optoelectronic properties. This review explores recent advancements in utilizing graphene in THz technology, focusing on two main aspects: THz molecular sensing and THz wave modulation. In molecular sensing, the environment-sensitive THz transmission and emission properties of graphene are utilized for enabling molecular adsorption detection and biomolecular sensing. This capability holds significant potential, from the detection of pesticides to DNA at high sensitivity and selectivity. In THz wave modulation, crucial for next-generation wireless communication systems, graphene demonstrates remarkable potential in absorption modulation when gated. Novel device structures, spectroscopic systems, and metasurface architectures have enabled enhanced absorption and wave modulation. Furthermore, techniques such as spatial phase modulation and polarization manipulation have been explored. From sensing to communication, graphene-based THz devices present a wide array of opportunities for future research and development. Finally, advancements in sensing techniques not only enhance biomolecular analysis but also contribute to optimizing graphene\'s properties for communication by enabling efficient modulation of electromagnetic waves. Conversely, developments in communication strategies inform and enhance sensing capabilities, establishing a mutually beneficial relationship.
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  • 文章类型: Journal Article
    在这项研究中,我们提出了第一个使用太赫兹(THz)感应的湿疹和牛皮癣患者的体内临床研究。使用手持THz扫描仪测量湿疹和牛皮癣患者,之前和之后的应用保湿霜。我们表明THz传感可以区分身体不同区域的干燥和健康皮肤。此外,使用THz光也可以观察和潜在评估使用保湿霜对皮肤的影响。
    In this study we present the first in vivo clinical study of patients with eczema and psoriasis using terahertz (THz) sensing. Eczema and psoriasis patients were measured using a handheld THz scanner, both before and after the application of moisturiser. We show that THz sensing can distinguish between dry and healthy skin in different regions of the body. Furthermore, the impact of applying moisturiser on the skin can also be observed and potentially evaluated using THz light.
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  • 文章类型: Journal Article
    有机-无机杂化钙钛矿的稳定性不足仍然是其在光电器件中广泛商业应用的重要障碍。老化现象深刻地影响基于钙钛矿的器件的光电性能。除了增强钙钛矿的稳定性,老化状态的实时检测,旨在监测衰老进程,对于基础研究和有机-无机杂化钙钛矿的商业化至关重要。在这项研究中,利用太赫兹时域光谱技术对钙钛矿的老化状态进行了实时研究。我们的分析一致显示,随着钙钛矿老化的增加,0.968THz处的吸收峰强度逐渐下降。此外,对钙钛矿老化过程中太赫兹吸收峰的强度和位置的变化进行了系统的讨论。这些发现有助于钙钛矿老化的实时评估,提供了一种有前途的方法来加快基于钙钛矿的光电器件的商业化。
    The inadequate stability of organic-inorganic hybrid perovskites remains a significant barrier to their widespread commercial application in optoelectronic devices. Aging phenomena profoundly affect the optoelectronic performance of perovskite-based devices. In addition to enhancing perovskite stability, the real-time detection of aging status, aimed at monitoring the aging progression, holds paramount importance for both fundamental research and the commercialization of organic-inorganic hybrid perovskites. In this study, the aging status of perovskite was real-time investigated by using terahertz time-domain spectroscopy. Our analysis consistently revealed a gradual decline in the intensity of the absorption peak at 0.968 THz with increasing perovskite aging. Furthermore, a systematic discussion was conducted on the variations in intensity and position of the terahertz absorption peaks as the perovskite aged. These findings facilitate the real-time assessment of perovskite aging, providing a promising method to expedite the commercialization of perovskite-based optoelectronic devices.
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  • 文章类型: Journal Article
    太赫兹光谱在水溶液中生物分子的研究中具有独特的优势。然而,水在太赫兹区具有很强的吸收能力。减少液体量可以减少对太赫兹波的干扰,可能,然而,影响测量精度。因此,平衡液体样品的量和水含量尤为重要。在这项工作中,设计了一种基于金属条的太赫兹超材料传感器,制作,并用于检测反胶束。反胶束中的水性约束环境可以提高太赫兹响应的信噪比。由于“水池”被困在反胶束中,DOPC(1,2-二油酰基-sn-甘油-3-磷酸胆碱)溶液和DOPC乳液的强度可以通过太赫兹光谱成功鉴定。结合超材料传感器,可以实现30GHz的明显频移以将DOPC乳液(5%)与DOPC溶液区分开。这种方法可以提供一种潜在的方法来提高检测缓冲溶液中微量元素的灵敏度。从而为生物分析应用提供了一个有价值的工具包。
    Terahertz spectroscopy has unique advantages in the study of biological molecules in aqueous solutions. However, water has a strong absorption capability in the terahertz region. Reducing the amount of liquid could decrease interference with the terahertz wave, which may, however, affect the measurement accuracy. Therefore, it is particularly important to balance the amount and water content of liquid samples. In this work, a terahertz metamaterial sensor based on metallic strips is designed, fabricated, and used to detect reverse micelles. An aqueous confinement environment in reverse micelles can improve the signal-to-noise ratio of the terahertz response. Due to \"water pool\" trapped in reverse micelles, the DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine) solution and DOPC emulsion can successfully be identified in intensity by terahertz spectroscopy. Combined with the metamaterial sensor, an obvious frequency shift of 30 GHz can be achieved to distinguish the DOPC emulsion (5%) from the DOPC solution. This approach may provide a potential way for improving the sensitivity of detecting trace elements in a buffer solution, thus offering a valuable toolkit toward bioanalytical applications.
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  • 文章类型: Journal Article
    太赫兹(THz)光谱学由于其低破坏性和由于其包含的丰富的分子指纹吸收特征而显示出用于物质检测的巨大潜力。然而,关于不同温度下物质的指纹检测的研究有限。这里,我们提出了一种THz超材料狭缝阵列传感器,该传感器利用局部表面等离子体激元来增强狭缝内的电场。可以通过温度调节来调制传输峰值频率。该方法能够在多个光谱频率点检测分子吸收特性,从而实现对特征分析物指纹谱的特异性和高灵敏度检测。此外,传感器支持在多个温度下检测物质,并灵敏地识别其吸收特性随温度的变化。我们的研究采用温度变化来实现痕量分析物的高灵敏度和特异性检测,为THz分子检测提供新的解决方案。
    Terahertz (THz) spectroscopy has demonstrated significant potential for substance detection due to its low destructiveness and due to the abundance of molecular fingerprint absorption signatures that it contains. However, there is limited research on the fingerprint detection of substances at different temperatures. Here, we propose a THz metamaterial slit array sensor that exploits localized surface plasmons to enhance the electric field within the slit. The transmission peak frequency can be modulated via temperature adjustments. This method enables the detection of molecular absorption characteristics at multiple spectral frequency points, thereby achieving a specific and highly sensitive detection of characteristic analyte fingerprint spectra. Additionally, the sensor supports the detection of substances at multiple temperatures and sensitively identifies changes in their absorption properties as a function of temperature. Our research has employed temperature variation to achieve a highly sensitive and specific detection of trace analytes, offering a new solution for THz molecular detection.
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  • 文章类型: Journal Article
    受使用泵浦探针设置研究相关电子材料的太赫兹光谱学的最新发展的启发,我们从基本的时间相关扰动理论出发,回顾了场理论形式主义,以计算中心对称系统中的有限频率非线性电光响应。我们将非线性当前内核表示为几个因果响应函数的总和。这些因果函数不能用摄动场论方法来评估,因为它们不是等高线。因此,我们将每个响应函数与相应的虚时间有序电流相关函数相关联,因为后者可以用威克定理分解。响应函数和相关函数之间的映射,适当地分析继续到真实频率,被证明是准确的。我们推导了非线性电流核满足的约束,并证明了非线性电导率的广义f和规则,所有这些都是粒子数守恒的结果。这些约束保证了非线性静态响应没有杂散。我们应用该理论来计算存在弱无序的非相互作用电子系统的规范不变非线性电导率。作为这种广义非线性响应的特例,我们讨论了它的三次谐波和瞬时太赫兹克尔信号。形式主义可用于计算电子系统(例如超导体)的对称破碎相中的非线性电导率,密度波和向列状态。
    Motivated by the recent developments in terahertz spectroscopy using pump-probe setups to study correlated electronic materials, we review the field theoretical formalism to compute finite frequency nonlinear electro-optical responses in centrosymmetric systems starting from basic time dependent perturbation theory. We express the nonlinear current kernel as a sum of several causal response functions. These causal functions cannot be evaluated using perturbative field theory methods, since they are not contour ordered. Consequently, we associate each response function with a corresponding imaginary time ordered current correlation function, since the latter can be factorized using Wick\'s theorem. The mapping between the response functions and the correlation functions, suitably analytically continued to real frequencies, is proven exactly. We derive constraints satisfied by the nonlinear current kernel and we prove a generalizedf-sum rule for the nonlinear conductivity, all of which are consequences of particle number conservation. The constraints guarantee that the nonlinear static responses are free from spurious divergences. We apply the theory to compute the gauge invariant nonlinear conductivity of a system of noninteracting electrons in the presence of weak disorder. As special cases of this generalized nonlinear response, we discuss its third harmonic and its instantaneous terahertz Kerr signals. The formalism can be used to compute the nonlinear conductivity in symmetry broken phases of electronic systems such as superconductors, density waves and nematic states.
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  • 文章类型: Journal Article
    吡嗪酰胺(PZA)是一种广泛使用的抗结核药物,但其溶解性差促使我们优化药物性能。共晶是一种通过分子间相互作用将活性药物成分(API)与共晶体形成剂(CCF)连接来改善其理化性质的有前途的技术。即使使用一系列烷基二羧酸来形成共晶结构,对分子间相互作用的作用的系统理解仍然缺失。因此,太赫兹(THz)光谱和量子化学计算相结合,以阐明普遍存在的超分子合成子的行为,如酸吡嗪的杂合成子,酸-酰胺和酰胺-酰胺的同型合成子,从能源的角度来看。计算势能以区分PZA-MA共晶多晶型物内的稳定性,并评估自由能以分别比较PZA-CCF共晶的溶解度。关于振动能量,THz光谱指纹在理论上被分配给特定的振动,并归因于基于振荡理论的超分子合成子的柔性变形。拉伸和扭曲模式主导着集体振动行为。它提供了一个有前途的工具,从其驱动力和有见地的指导来评估共晶性能,以发现新的药物共晶。
    Pyrazinamide (PZA) is a widely-used anti-tuberculosis pharmaceutical, but its poor solubility prompts us to optimize pharmaceutical performance. Cocrystallization is a promising technique to improve physiochemical properties of active pharmaceutical ingredient (API) by connecting it with cocrystal former (CCF) via intermolecular interactions. Even though a series of alkyl dicarboxylic acids are employed to form cocrystal structures, systematic understanding on the role of intermolecular interactions is still missing. Therefore, terahertz (THz) spectroscopy and quantum chemical calculation are combined to elucidate the behavior of ubiquitous supramolecular synthons, such as hetero-synthons of acid-pyrazine, acid-amide and homo-synthon of amide-amide, from energy\'s view. Potential energy is calculated to differentiate the stability within polymorphs of PZA-MA cocrystal and free energy is evaluated to compare the solubility of PZA-CCF cocrystals respectively. With regard to vibrational energy, THz spectral fingerprints are theoretically assigned to specific vibrations and attributed to the flexibility deformation of supramolecular synthons based on oscillation theory, where stretching and twisting modes dominate the collective vibrational behavior. It provides a promising tool to evaluate cocrystal performance from its driving force and insightful guidance to discover new pharmaceutical cocrystals.
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  • 文章类型: Journal Article
    由铁磁金属层F和重金属层H组成的薄膜堆叠F|H是自旋电子模型系统。这里,我们提出了一种在太赫兹频率下测量F和H之间的层X上的超宽带自旋电导的方法,这是自旋输运动力学的固有频率。我们将我们的方法应用于厚度d=0-6的MgO隧穿势垒。在时域中,自旋电导Gs具有两个分量。瞬时特征来自诸如相干自旋隧穿的过程。值得注意的是,寿命更长的成分是MgO缺陷态介导的非相干共振自旋隧道的标志,因为它的弛豫时间随d单调增长,在d=6.0µ时达到270fs。我们的结果与分析模型完全一致。他们表明,太赫兹自旋电导光谱将为各种自旋纳米结构中的超快自旋传输提供新的相关见解。
    Thin-film stacks F|H consisting of a ferromagnetic-metal layer F and a heavy-metal layer H are spintronic model systems. Here, we present a method to measure the ultrabroadband spin conductance across a layer X between F and H at terahertz frequencies, which are the natural frequencies of spin-transport dynamics. We apply our approach to MgO tunneling barriers with thickness d = 0-6 Å. In the time domain, the spin conductance Gs has two components. An instantaneous feature arises from processes like coherent spin tunneling. Remarkably, a longer-lived component is a hallmark of incoherent resonant spin tunneling mediated by MgO defect states, because its relaxation time grows monotonically with d to as much as 270 fs at d = 6.0 Å. Our results are in full agreement with an analytical model. They indicate that terahertz spin-conductance spectroscopy will yield new and relevant insights into ultrafast spin transport in a wide range of spintronic nanostructures.
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  • 文章类型: Journal Article
    视网膜希夫碱的光诱导全反式至13顺式异构化代表了细菌视紫红质(BR)反应循环中的超快第一步。广泛的实验和理论工作已经通过与基态的锥形相交解决了激发态动力学和异构化。在相互矛盾的分子图片中,激发态势能表面已被建模为与基态相交的纯S[公式:见文本]状态,或在涉及S[公式:见文本]和S[公式:见文本]状态的3状态图片中。这里,光激发系统通过两个交叉区域返回到基态。希夫碱在S[公式:见正文]和S[公式:见正文]状态下的电偶极矩差异很大,并且,因此,它的测量允许评估激发态电势的特征。我们应用超快太赫兹(THz)Stark光谱的方法来测量野生型BR和BRD85T突变体在电子激发下的电偶极子变化。电子吸收的完全可逆的瞬态展宽和光谱偏移是由几兆伏/厘米的皮秒THz场引起的,并由120fs光学探测脉冲映射。对于两种BR变体,我们推导出5的中等电偶极子变化[公式:见正文]1德拜,明显小于激发态的纯S[公式:见文字]-字符的预测值。相比之下,S[公式:参见正文]-在探测脉冲持续时间内激发态动力学的混合和时间平均给出了与实验一致的偶极变化。我们的结果支持3状态模型中由S[公式:见文本]和S[公式:见文本]状态相互作用控制的电子和核动力学图。
    The photoinduced all-trans to 13-cis isomerization of the retinal Schiff base represents the ultrafast first step in the reaction cycle of bacteriorhodopsin (BR). Extensive experimental and theoretical work has addressed excited-state dynamics and isomerization via a conical intersection with the ground state. In conflicting molecular pictures, the excited state potential energy surface has been modeled as a pure S[Formula: see text] state that intersects with the ground state, or in a 3-state picture involving the S[Formula: see text] and S[Formula: see text] states. Here, the photoexcited system passes two crossing regions to return to the ground state. The electric dipole moment of the Schiff base in the S[Formula: see text] and S[Formula: see text] state differs strongly and, thus, its measurement allows for assessing the character of the excited-state potential. We apply the method of ultrafast terahertz (THz) Stark spectroscopy to measure electric dipole changes of wild-type BR and a BR D85T mutant upon electronic excitation. A fully reversible transient broadening and spectral shift of electronic absorption is induced by a picosecond THz field of several megavolts/cm and mapped by a 120-fs optical probe pulse. For both BR variants, we derive a moderate electric dipole change of 5 [Formula: see text] 1 Debye, which is markedly smaller than predicted for a neat S[Formula: see text]-character of the excited state. In contrast, S[Formula: see text]-admixture and temporal averaging of excited-state dynamics over the probe pulse duration gives a dipole change in line with experiment. Our results support a picture of electronic and nuclear dynamics governed by the interaction of S[Formula: see text] and S[Formula: see text] states in a 3-state model.
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