Temperature-dependent far-infrared spectra of single crystals of high explosives using terahertz time-domain spectroscopy

Survey spectra of single-crystal HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and PETN (pentaerythritol tetranitrate) were acquired in the region from 10 to 80 cm(-1) using terahertz time-domain spectroscopy. The spectra were taken at temperatures ranging from 8.4 to 300 K. Generally, the spectra show multiple absorption peaks in the range 50-80 cm(-1), with PETN (110) showing strong absorption features at room temperature. RDX (210) is the most notable in the region 10-40 cm(-1), showing multiple spectral features, while HMX (010) shows a very broad absorption at 47.8 cm(-1) with a fwhm of 37.3 cm(-1). Future plans include polarization-dependent investigations for multiple crystallographic orientations over an increased spectral range and higher-level theoretical calculations.     

Classical theory of two-dimensional time-domain terahertz spectroscopy

A general theoretical framework of two-dimensional time-domain second-order and third-order terahertz spectroscopy has been presented. The theoretical treatment is based on a classical and phenomenological model with weak nonlinearities. Three types of nonlinearity sources, anharmonicity, nonlinear coupling, and nonlinear damping, were considered. The second-order THz spectroscopy has an exact correspondence to fifth-order off-resonance Raman spectroscopy, and it has been shown that the present treatment gives exactly the same results as of the quantum mechanical theory under the weak nonlinearity condition. General expressions for the nonlinear signal have been obtained for a single-mode system, and numerical calculations for delta-function incident terahertz pulses were shown. For the third-order signal, two-level systems were also considered for comparison. Contributions of two types of incident pulse sequences have been studied separately in the third-order signals. Profiles of the two-dimensional signals were found to depend on the origin and order of the nonlinearity and also on the pulse sequence. The results of the present study show that the two-dimensional signal features of second- and third-order nonlinear terahertz spectroscopy can clarify the nature of the system which is not accessible using linear spectroscopy.     

Orientation dependent far-infrared terahertz absorptions in single crystal pentaerythritol tetranitrate (PETN) using terahertz time-domain spectroscopy

Terahertz time-domain spectroscopy (THZ-TDS) has been used to measure the absorption spectra in the range 7-100 cm(-1) (0.2-3 THz) of single crystal pentaerythritol tetranitrate (PETN). Absorption was measured in transmission mode as a function of incident polarization with the incident and transmitted wave vectors oriented along the crystallographic directions [100], <10(a/c)(2)>, and <110>. Samples were rotated with respect to the incident polarization while absorption was measured at both 300 and 20 K. Comparatively minor differences were observed among the three orientations. Two broad absorptions at 72 and >90 cm(-1), and several weaker absorptions at 36, 55, 80, and 82 cm(-1), have been observed at cryogenic temperatures.     

Intermolecular vibrational mode of the benzoic acid dimer in solution observed by terahertz time-domain spectroscopy

The low-frequency modes of the benzoic acid (BA) dimer and its analogues in carbon tetrachloride (CCl(4)) have been investigated by terahertz time-domain spectroscopy. The solute spectrum is obtained by subtracting the solvent contribution from that of the solution. The difference spectrum of BA in CCl(4) has a broad band with a peak at 68 cm(-1). To assign the observed band, the spectrum is compared with spectra of other aromatic molecules, such as benzene and phenol in addition to p-methyl BA and deuterated BA species (BA-d(OH) and BA-d(5)) in CCl(4). The band at 68 cm(-1) is assigned to the cogwheel mode of the BA dimer. Density functional theory calculations also support this assignment. Finally, spectral lineshape analysis based on the multimode Brownian oscillator model is applied to the THz spectra for all the samples.     

Cure monitoring of two-component epoxy adhesives by terahertz time-domain spectroscopy

We report nondestructive measurements of the properties of two-component epoxy adhesives at terahertz wavelengths using a transmissive time-domain spectroscopy system. The results show that the different epoxies have measurably different THz properties, that the changes which occur during the curing process can be monitored by measurements of their refractive index and absorption at terahertz wavelengths, and that this technique is sensitive enough to record changes in the optical material parameters during the postcuring process.     

Nondestructive examination of polymethacrylimide composite structures with terahertz time-domain spectroscopy

THz reflective time domain spectroscopy (THz-RTDS) has been considered as an effective method to detect hidden objects with potential for supplementing other NDE technologies for foam composite adhesive structure debonding defects. PMI (Polymethacrylimide) is a heat-resistant foam material, with the highest strength and stiffness to weight ratio. It is widely used in various parts of airplanes, especially the wing leading edge and rudder, landing gear doors, wing-body/wingtip fairings and so on. We analyzed the features of adhesive debonding defect based mainly on the variation of the time-domain wave form and compared with the inclusion defect. The quantification of degrees of adhesive debonding can be readily achieved with THz-RTDS images based on the delay of the wave front and the main reflection time-domain waveforms. Typical accuracy of about 100 μm was achieved.     

Measurement of coherent terahertz radiation for time-domain spectroscopy and imaging

A high-power terahertz (THz) source for THz time-domain spectroscopy (THz-TDS) and THz imaging has been developed based on an S-band compact electron linac at the National Institute of Advanced Industrial Science and Technology (AIST). A THz pulse was generated as coherent synchrotron radiation (CSR) from an ultra-short electron bunch and expected to have peak power of kW-order with frequency range of 0.1–2 THz. The electro-optic (EO) sampling method with a ZnTe crystal for the THz pulse measurement has been prepared for THz-TDS system. The timing measurement between the THz pulse and a probe laser was carried out. A preliminary experiment of THz transmission imaging of an integrated circuit (IC) card has been successfully demonstrated using the THz CSR pulse and a W-band rf detector. The imaging result was experimentally compared with a result of X-ray imaging. It is confirmed that its intensity and stability are enough to perform for the THz applications.     

Far-infrared characteristics of ZnS nanoparticles measured by terahertz time-domain spectroscopy

The optical and dielectric properties of ZnS nanoparticles are studied by use of terahertz time-domain spectroscopy (THz-TDS) over the frequency range from 0.3 to 3.0 THz. The effective medium approach combined with the pseudo-harmonic model of the dielectric response, where nanoparticles are embedded in the host medium, provides a good fit on the experimental results. The extrapolation of the measured data indicates that the absorption is dominated by the transverse optical mode localized at 11.6+/-0.2 THz. Meanwhile, the low-frequency phonon resonance of ZnS nanoparticles is compared with the single-crystal ZnS. The THz-TDS clearly reveals the remarkable distinction in the low-frequency phonon resonances between ZnS nanoparticles and single-crystal ZnS. The results demonstrate that the acoustic phonons become confined in small-size nanoparticles.     

Conductivity of solvated electrons in hexane investigated with terahertz time-domain spectroscopy

We present investigations of the transient photoconductivity and recombination dynamics of quasifree electrons in liquid n-hexane and cyclohexane performed using terahertz time-domain spectroscopy (THz-TDS). Quasifree electrons are generated by two-photon photoionization of the liquid using a femtosecond ultraviolet pulse, and the resulting changes in the complex conductivity are probed by a THz electromagnetic pulse at a variable delay. The detection of time-domain wave forms of the THz electric field permits the direct determination of both the real and the imaginary part of the conductivity of the electrons over a wide frequency range. The change in conductivity can be described by the Drude model, thus yielding the quasifree electron density and scattering time. The electron density is found to decay on a time scale of a few hundred picoseconds, which becomes shorter with increasing excitation density. The dynamics can be described by a model that assumes nongeminate recombination between electrons and positive ions. In addition, a strong dependence of the quasifree electron density on temperature is observed, in agreement with a two-state model in which the electron may exist in either a quasifree or a bound state.     

Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging

Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15–4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.     

Far-infrared investigation of kaolinite and halloysite intercalates using terahertz time-domain spectroscopy

Two clay minerals from the kaolin group, namely well-ordered kaolinite and poorly ordered halloysite, were investigated by terahertz time-domain spectroscopy (THz-TDS). Both clay samples were used for preparation of their respective intercalates using dimethyl sulfoxide (DMSO) and potassium acetate (KAc) with water. The intercalates were also characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The dielectric behaviour of clay samples was investigated in the far-infrared region of 0.2–2.7 THz corresponding to about 6.7–89.9 cm⁻¹. The frequency dependence of the power absorption coefficient revealed clear absorption bands for DMSO intercalates but not for KAc with water. For kaolinite – DMSO intercalate a distinct doublet at 1.70 THz (56.6 cm⁻¹) and 1.88 THz (62.6 cm⁻¹), and for halloysite – DMSO intercalate a single broad band centred around 1.72 THz (57.3 cm⁻¹) were found. These bands are reported for the first time in this type of intercalation substances and indicate the application potential of THz time-domain spectroscopy for use in the investigation and detection of chemical behaviour of molecular species introduced into the interlayer space of layered substances such as clays and clay minerals. Additionally, the qualitative characteristics of observed bands of DMSO intercalates in the THz region reasonably resembled the structural order/disorder of used kaolinite and halloysite samples.     

Characterizing polymorphism and crystal transformation of polylactide by terahertz time-domain spectroscopy

Terahertz time-domain spectroscopy (THz-TDS), which has been proved to show promising application in complex polymer systems, was employed to investigate the polymorphism phenomenon and crystal transformation of polylactide (PLA) in this study. The THz-TDS shows sensitive response on the crystal structure. The α'-form, α-form and stereocomplex crystals exhibit absorption peaks of lattice vibration at 1.82, 2.01 and 2.09 THz, respectively. THz-TDS has no direct chirality identification on the difference between poly (d-lactide) (PDLA) and poly(l-lactide) (PLLA). However, the PLA stereocomplex shows an extra and distinctive absorption peak at 1.43 THz compared with homo-PLA, and the peak was proved to be stemmed from the collective vibration of L-lactic unit and D-lactic unit pairs connecting by hydrogen bonds. This is the first time that THz-TDS has been proved to be of great potential in identification of polymer stereocomplex crystal. Also, the α'→α crystal transformation of PLA were intuitively investigated at 120 °C using THz-TDS, while the transformation rate was quite slow.     

Detecting a sodium chloride ion pair in ice using terahertz time-domain spectroscopy.

The hydrogen bond resonance of a sodium chloride (NaCl) ion pair trapped in aqueous ice has been observed by transmission terahertz time-domain spectroscopy. The absorption peak of a sodium chloride ion pair in ice is 1.65 THz at 83 K. By investigating the interaction of the cation and anion with other chemical compounds, we deduce that the absorption peak originates from the hydrogen bond resonance of sodium chloride and water molecules. The charge redistribution that occurs when other ion pairs are added to aqueous salt solution changes the absorption spectrum. Furthermore, the results also indicate that simple molecules such as sodium halides have fingerprints in the terahertz region when the ions are trapped in ice. NaCl ion pairs in seawater and in Ringer's solution were examined.     

Growth and spectroscopy studies of ADP single crystals with l-glutamine and l-cysteine amino acids

Ammonium dihydrogen orthophosphate (ADP) crystals were grown with l-glutamine C₅H₁₀N₂O₃ (gln) and l-cysteine C₃H₇NO₂S (cys) amino acids, with polar side-chains, as additives at 4% molar concentrations. X-ray diffractograms, vibrational FT-IR, and Raman and NMR MAS of ³¹P, ¹H and of pure and treated compounds were recorded at room temperature and interpreted. A lift of degeneracies of the ν₄ asymmetric bending modes of both PO₄ and NH₄ tetrahedron species, as well as a shift of the wavenumbers of some of their internal modes was observed. At the same time, some characteristic vibrational modes of the organic molecules appeared. However, NMR results show a little shift of the resonance of the phosphorus and hydrogen nucleus, associated with some shoulders for this latter. The presence of the organic molecules was also revealed by ¹³C MAS NMR. These observations indicate that the host-additives interactions were achieved.     

Probing structural transition and guest dynamics of hydroquinone clathrates by temperature-dependent terahertz time-domain spectroscopy

The structural transition from hydroquinone clathrates to crystalline α-form hydroquinone was observed up to the range of 3 THz frequency as a function of temperatures. We found that all three hydroquinone clathrates, CO(2)-, CH(4)-, and CO(2)/CH(4)-loaded hydroquinone clathrates, transform into the α-form hydroquinone at around 102 ± 7 °C. The resonance peak of the CO(2)-loaded hydroquinone clathrate at 2.15 THz decreases with increasing temperature, indicating that CO(2) guest molecules are readily released from the host framework prior to the structural transformation. This reveals that the hydroquinone clathrates may transform into the stable α-form hydroquinone via the metastable form of guest-free clathrate, which depends on guest molecules enclathrated in the cages of the host frameworks. A strong resonance of the α-form hydroquinone at 1.18 THz gradually shifts to the low frequency with increasing temperature and shifts back to the high frequency with decreasing temperature.     

Measuring acetic acid dimer modes by ultrafast time-domain Raman spectroscopy

Acetic acid is capable of forming strong multiple hydrogen bonds and therefore different dimeric H-bonded structures in neat liquid phase and in solutions. The low frequency Raman spectra of acetic acid (neat, in aqueous solution and as a function of temperature) were obtained by ultrafast time and polarization resolved optical Kerr effect (OKE) measurements. Isotropic OKE measurements clearly reveal a specific totally symmetric mode related to the dimeric structure H-bond stretching mode. The effects of isotope substitution, water dilution and temperature on this mode were investigated. These results together with anisotropic OKE measurements and density functional theory calculations for a number of possible dimers provide strong evidence for the cyclic dimer structure being the main structure in liquid phase persisting down to acetic acid concentrations of 10 M. Some information about the dimer structure and concentration dependence was inferred.     

An algorithm to identify the existence and reproducibly obtain single crystals of salts and mixed crystals of amino acids suitable for single crystal XRD and Raman spectroscopy experiments

An algorithm is proposed to reproducibly obtain single crystals of salts and mixed crystals of amino acids with dicarboxylic acids and other small organic molecules. The resulting crystals are of high quality and have good faceting, which makes them suitable for single crystal XRD and Raman spectroscopic (including polarized radiation) experiments. The ease of the implementation and the possibility to reproduce the crystallization using equipment and materials that are available at virtually every laboratory are the hallmarks of the proposed algorithm, which involves two stages of work. During the first stage, the original components are screened, quickly and easily, to find new phases. The aim of the second stage is to obtain single crystals that meet the requirements of different research methods. An ideal case is the one whereby it is possible to control the size of well-faceted spaced apart crystals that grow within a few hours and are easy to separate from the surface.     

Analytical terahertz spectroscopy.

Recent progress in analytical terahertz (THz) spectroscopy is reviewed with illustrative examples showing that it is an effective method for detecting and identifying intermolecular interactions in chemical compounds, such as hydrogen bonds. The unique and characteristic properties of THz waves, their significance to both science and industry, and the bases of one of the successful fields of analytical THz spectroscopy, namely THz time-domain spectroscopy and THz imaging for chemical analysis, are described. Preliminary quantitative studies are presented to show the potential of THz spectroscopy for the detection and identification of intermolecular hydrogen bonds in unknown mixture samples. The selective detection of intramolecular hydrogen bonds and the detection of intramolecular interactions in ice are also introduced. Some brief remarks are provided on future developments, the main issues, and the prospects for analytical THz spectroscopy.     

In silico prediction of deleterious single amino acid polymorphisms from amino acid sequence

Molecular cause of human disease retains as one of the most attractive scientific research targets for decades. An effective approach toward this topic is analysis and identification of disease-related amino acid polymorphisms. In this work, we developed a concise and promising deleterious amino acid polymorphism identification method SeqSubPred based on 44 features solely extracted from protein sequence. SeqSubPred achieved surprisingly good predictive ability with accuracy (0.88) and area under receiver operating characteristic (0.94) without resorting to homology or evolution information, which is frequently used in similar methods and usually more complex and time-consuming. SeqSubPred also identified several critical sequence features obtained from random forests model, and these features brought some interesting insights into the factors affecting human disease-related amino acid substitutions. The online version of SeqSubPred method is available at montana.informatics.indiana.edu/cgi-bin/seqmut/seqsubpred.cgi