Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH3O13CH3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.

CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, 12CH3–16O–12CD3 (DME-d3) and 12CD3–16O–12CD3 (DME-d6), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d6 belongs to the G36 group, as the most abundant isotopologue 12CH3–16O–12CH3 (DME-h6), while DME-d3 is a G18 species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d6. Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N – 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d3 intensities and the band positions of the torsional overtones.

Highly correlated ab initio study of the far infrared spectra of methyl acetate

Highly correlated ab initio calculations (CCSD(T)) are used to compute gas phase spectroscopic parameters of three isotopologues of the methyl acetate (CH3COOCH3, CD3COOCH3, and CH3COOCD3), searching to help experimental assignments and astrophysical detections. The molecule shows two conformers cis and trans separated by a barrier of 4457 cm−1. The potential energy surface presents 18 minima that intertransform through three internal rotation motions. To analyze the far infrared spectrum at low temperatures, a three-dimensional Hamiltonian is solved variationally. The two methyl torsion barriers are calculated to be 99.2 cm−1 (C–CH3) and 413.1 cm−1 (O–CH3), for the cis-conformer. The three fundamental torsional band centers of CH3COOCH3 are predicted to lie at 63.7 cm−1 (C–CH3), 136.1 cm−1 (O–CH3), and 175.8 cm−1 (C–O torsion) providing torsional state separations. For the 27 vibrational modes, anharmonic fundamentals and rovibrational parameters are provided. Computed parameters are compared with those fitted using experimental data.

Determinación de la higroscopicidad y comportamiento termodinámico de la madera juvenil y madura a través de sus isotermas de sorción

La respuesta higroscópica de la madera varía a lo largo de la dirección radial del árbol. El aumento de corta de ejemplares jóvenes y el uso de troncos de pequeños diámetros en la industria de los productos forestales, hacen preciso estudiar el comportamiento higroscópico tanto de la madera juvenil como de la madura. Su determinación proporciona información para comprender los mecanismos de sorción. Asimismo, la obtención de las propiedades termodinámicas de ambos tipos de madera facilita la modelización de procesos industriales como el secado o el encolado. En el presente trabajo, se ha comparado el comportamiento higroscópico y las propiedades termodinámicas de la madera juvenil y madura de Abies pinsapo Boissier, Abies alba Mill., Pinus canariensis C. Sm. ex DC., Pinus nigra Arnold, Pinus uncinata Mill. ex Mirb. y Pinus pinea L. Para este propósito se han utilizado las isotermas de sorción obtenidas mediante el método tradicional de sales saturadas descrito por COST Action E8 a 15, 35 y 50ºC en Abies pinsapo, Abies alba, Pinus nigra, Pinus uncinata y Pinus pinea, y a 35 y 50ºC en Pinus canariensis. Igualmente, se ha empleado el equipo dynamic vapor sorption (DVS) en la obtención de las isotermas de Pinus pinea a 35 y 50ºC. El ajuste de las curvas se ha realizado mediante el modelo Guggenheim, Anderson y de Boer-Dent (GAB), cumpliendo todas las muestras los criterios de aceptación establecidos. En el estudio de las isotermas se ha calculado el coeficiente y área de histéresis entre el proceso de adsorción y desorción para cada una de las muestras. Con el fin de comprender el comportamiento higroscópico experimentado por cada madera se ha determinado la composición química, espectros de infrarrojos (FTIR) y difractogramas de rayos X de cada una. Los parámetros termodinámicos - calor isostérico neto y total heat of wetting - se han obtenido a partir de las isotermas de sorción mediante el método de integración de la ecuación de Clausius-Clapeyron. Finalmente, se han comparado los datos obtenidos con el método tradicional de sales saturadas y con dynamic vapor sorption con el propósito de conocer la existencia de similitudes entre ambas metodologías. Los resultados mostraron que los puntos de equilibrio son, en la mayor parte de los casos, superiores en la madera madura frente a la juvenil, y por tanto las isotermas de la madera madura se encuentran siempre por encima de las de la juvenil, debido principalmente a la composición química. Respecto a las propiedades termodinámicas, se ha determinado que la energía involucrada en los procesos de sorción es superior en la madera madura que en la madera juvenil, siendo mayor en el proceso de desorción frente al de adsorción. En la comparación de las metodologías de sales saturadas y dynamic vapor sorption no se han detectado casi diferencias significativas en el proceso de adsorción, mientras que sí se han obtenido en el de desorción. ABSTRACT The hygroscopic response of wood varies throughout the radial direction of the tree. The longer cut of young trees and the use of small-diameter trunks in the forest product industry make it necessary to study the hygroscopic behaviour of both juvenile and mature wood. Determining this behaviour in both types of wood provides information for understanding the sorption mechanisms. Similarly, obtaining the thermodynamic properties of juvenile and mature wood facilitates modelling of industrial processes such as drying and bonding. In this study a comparison was made of the hygroscopic behaviour and thermodynamic properties of juvenile and mature wood of Abies pinsapo Boissier, Abies alba Mill., Pinus canariensis C. Sm. ex DC., Pinus nigra Arnold, Pinus uncinata Mill. ex Mirb. and Pinus pinea L. This was done by obtaining the sorption isotherms using the traditional saturated salt method described by COST Action E8 at 15, 35 and 50ºC in Abies pinsapo, Abies alba, Pinus nigra, Pinus uncinata and Pinus pinea, and at 35 and 50ºC in Pinus canariensis. In addition, dynamic vapour sorption (DVS) was used to obtain the isotherms of Pinus pinea at 35 and 50ºC. The curves were fitted using the Guggenheim, Anderson and de Boer- Dent (GAB) model and all samples met the established acceptance criteria. In the study of the isotherms, the hysteresis coefficient and area of the hysteresis loop between adsorption and desorption were calculated for each sample. To understand the hygroscopic behaviour of juvenile and mature wood, the chemical composition, infrared spectra (FTIR) and X-ray diffractograms of each type of wood were determined. The thermodynamic parameters - net isosteric heat and total heat of wetting - were obtained from the sorption isotherms by applying the integration method of the Clausius-Clapeyron equation. The data obtained using the traditional saturated salt method and with dynamic vapour sorption were compared to determine the similarities between the two methods. The results showed that the equilibrium points are greater in the mature wood than in the juvenile wood in most cases, and therefore the mature wood isotherms are always above the juvenile wood isotherms, mainly because of the chemical composition. As regards the thermodynamic properties, it was determined that the energy involved in the sorption processes is greater in the mature wood than in the juvenile wood, and is greater in the desorption process than in the adsorption process. On comparing the saturated salt and dynamic vapour sorption methods, almost no significant differences were detected in the adsorption process, but significant differences were obtained in the desorption process.

Near infrared high efficiency InAs/GaAsSb QDLEDs: band alignment and carrier recombination mechanisms

The development of high efficiency laser diodes (LD) and light emitting diodes (LED) covering the 1.0 to 1.55 μm region of the spectra using GaAs heteroepitaxy has been long pursued. Due to the lack of materials that can be grown lattice-macthed to GaAs with bandgaps in the 1.0 to 1.55 μm region, quantum wells (QW) or quantum dots (QD) need be used. The most successful approach with QWs has been to use InGaAs, but one needs to add another element, such as N, to be able to reach 1.3/1.5μm. Even though LDs have been successfully demonstrated with the QW approach, using N leads to problems with compositional homogeneity across the wafer, and limited efficiency due to strong non-radiative recombination. The alternative approach of using InAs QDs is an attractive option, but once again, to reach the longest wavelengths one needs very large QDs and control over the size distribution and band alignment. In this work we demonstrate InAs/GaAsSb QDLEDs with high efficiencies, emitting from 1.1 to 1.52 μm, and we analyze the band alignment and carrier loss mechanisms that result from the presence of Sb in the capping layer.

On-line measurement of soil properties without direct spectral response in near infrared spectral range

So far, the majority of reports on on-line measurement considered soil properties with direct spectral responses in near infrared spectroscopy (NIRS). This work reports on the results of on-line measurement of soil properties with indirect spectral responses, e.g. pH, cation exchange capacity (CEC), exchangeable calcium (Caex) and exchangeable magnesium (Mgex) in one field in Bedfordshire in the UK. The on-line sensor consisted of a subsoiler coupled with an AgroSpec mobile, fibre type, visible and near infrared (vis–NIR) spectrophotometer (tec5 Technology for Spectroscopy, Germany), with a measurement range 305–2200 nm to acquire soil spectra in diffuse reflectance mode. General calibration models for the studied soil properties were developed with a partial least squares regression (PLSR) with one-leave-out cross validation, using spectra measured under non-mobile laboratory conditions of 160 soil samples collected from different fields in four farms in Europe, namely, Czech Republic, Denmark, Netherland and UK. A group of 25 samples independent from the calibration set was used as independent validation set. Higher accuracy was obtained for laboratory scanning as compared to on-line scanning of the 25 independent samples. The prediction accuracy for the laboratory and on-line measurements was classified as excellent/very good for pH (RPD = 2.69 and 2.14 and r2 = 0.86 and 0.78, respectively), and moderately good for CEC (RPD = 1.77 and 1.61 and r2 = 0.68 and 0.62, respectively) and Mgex (RPD = 1.72 and 1.49 and r2 = 0.66 and 0.67, respectively). For Caex, very good accuracy was calculated for laboratory method (RPD = 2.19 and r2 = 0.86), as compared to the poor accuracy reported for the on-line method (RPD = 1.30 and r2 = 0.61). The ability of collecting large number of data points per field area (about 12,800 point per 21 ha) and the simultaneous analysis of several soil properties without direct spectral response in the NIR range at relatively high operational speed and appreciable accuracy, encourage the recommendation of the on-line measurement system for site specific fertilisation.

Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

Detection and quantification of peanut traces in wheat flour by near infrared hyperspectral imaging spectroscopy using principal-component analysis

The use of a common environment for processing different powder foods in the industry has increased the risk of finding peanut traces in powder foods. The analytical methods commonly used for detection of peanut such as enzyme-linked immunosorbent assay (ELISA) and real-time polymerase chain reaction (RT-PCR) represent high specificity and sensitivity but are destructive and time-consuming, and require highly skilled experimenters. The feasibility of NIR hyperspectral imaging (HSI) is studied for the detection of peanut traces down to 0.01% by weight. A principal-component analysis (PCA) was carried out on a dataset of peanut and flour spectra. The obtained loadings were applied to the HSI images of adulterated wheat flour samples with peanut traces. As a result, HSI images were reduced to score images with enhanced contrast between peanut and flour particles. Finally, a threshold was fixed in score images to obtain a binary classification image, and the percentage of peanut adulteration was compared with the percentage of pixels identified as peanut particles. This study allowed the detection of traces of peanut down to 0.01% and quantification of peanut adulteration from 10% to 0.1% with a coefficient of determination (r2) of 0.946. These results show the feasibility of using HSI systems for the detection of peanut traces in conjunction with chemical procedures, such as RT-PCR and ELISA to facilitate enhanced quality-control surveillance on food-product processing lines.