Iron XII to XXII spectra measurements between 250 and 400 angstrom

This paper reports laboratory measurements of the spectrum of the most abundant transition Fe ions in the universe. Spectrum of iron of low-lying excited states has been observed in the wavelength range 250-400 angstrom at Chinese Institute of Atomic Energy on the HI-13 tandem accelerator with beams of 130 MeV. A number of spectral lines have been mainly classified as transitions of magnesium-, sodium-, neon-, fluorine-like ions. A total of 54 lines have been measured. Most of them have been mainly ascribed to 3s3p(k)-3p(k+1), 3s(2)3p(k)-3s3p(k+1), 2p(5)3s-2p(5)3p, 3s3d-3p3d and 2p(5)3p-2p(5)3d resonance transitions. These spectral lines have been identified, among which 21 are new and accurately measured. The analysis of the spectra was based on a comparison with other experimental results and calculated values. (c) 2010 Elsevier Ltd. All rights reserved.

Self-assembled monolayer growth of octanol on mica: Atomic force microscopy and Fourier-transform infrared spectroscopy studies

The growth kinetics of self-assembled monolayers formed by exposing freshly cleaved mica to octanol solution has been studied by atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). AFM images of samples immersed in octanol for varying exposure times showed that before forming a complete monolayer the octanol molecules aggregated in the form of small islands on the mica surface. With the proceeding of immersion, these islands gradually grew and merged into larger patches. Finally, a close-packed film with uniform appearance and few defects was formed. The thickness of the final film showed 0.8 nm in height, which corresponded to the 40degrees tilt molecular conformation of the octanol monolayer. The growth mechanisms consisted of nucleation, growth, and coalescence of the submonolayer films. The growth process was also confirmed by FTIR. And the surface coverage of the submonolayer islands estimated from AFM images and FTIR spectra as a function of immersion time was quite consistent.

Characteristics in frequency domain by inductively coupled plasma atomic emission spectrometry with charge injection detection

The charactesistics of two-dimension spectra obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES) with charge injection detection (CID) in frequency domain were studied in the present paper. The measurement spectra were Fourier transformed and the frequency distribution of the spectra was obtained. Results showed that the spectra in frequency domain could he divided into two parts:high frequency and low frequency signals. The later stood for measurement spectra and the former for background and noises. However, the high frequecny signals could not be smoothed simply to reduce noises because the background was deteriorated even though the spectral signal did not change significantly.

APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

Extreme ultraviolet emission lines of Ca XV in solar and laboratory spectra

New R-matrix calculations of electron impact excitation rates in Ca XV are used to derive theoretical electron density diagnostic emission line intensity ratios involving 2s(2)2p(2)- 2s2p(3) transitions, specifically R-1 = I(208.70 Angstrom)/I(200.98 Angstrom), R-2 = I(181.91 Angstrom)/I(200.98 Angstrom), and R-3 = I(215.38 Angstrom)/I(200.98 Angstrom), for a range of electron temperatures (T-e = 10(6.4)-10(6.8) K) and densities (Ne = 10(9)-10(13) cm(-3)) appropriate to solar coronal plasmas. Electron densities deduced from the observed values of R-1, R-2, and R-3 for several solar flares, measured from spectra obtained with the Naval Research Laboratory's S082A spectrograph on board Skylab, are found to be consistent. In addition, the derived electron densities are in excellent agreement with those determined from line ratios in Ca XVI, which is formed at a similar electron temperature to Ca XV. These results provide some experimental verification for the accuracy of the line ratio calculations, and hence the atomic data on which they are based. A set of eight theoretical Ca XV line ratios involving 2s(2)2p(2)-2s2p(3) transitions in the wavelength range similar to140-216 Angstrom are also found to be in good agreement with those measured from spectra of the TEXT tokamak plasma, for which the electron temperature and density have been independently determined. This provides additional support for the accuracy of the theoretical line ratios and atomic data.

Fe XIII emission lines in active region spectra obtained with the Solar Extreme-Ultraviolet Research Telescope and Spectrograph

Recent fully relativistic calculations of radiative rates and electron impact excitation cross-sections for FeXIII are used to generate emission-line ratios involving 3s23p2-3s3p3 and 3s23p2-3s23p3d transitions in the 170-225 and 235-450 Å wavelength ranges covered by the Solar Extreme-Ultraviolet Research Telescope and Spectrograph (SERTS). A comparison of these line ratios with SERTS active region observations from rocket flights in 1989 and 1995 reveals generally very good agreement between theory and experiment. Several new FeXIII emission features are identified, at wavelengths of 203.79, 259.94, 288.56 and 290.81 Å. However, major discrepancies between theory and observation remain for several FeXIII transitions, as previously found by Landi and others, which cannot be explained by blending. Errors in the adopted atomic data appear to be the most likely explanation, in particular for transitions which have 3s23p3d1D2 as their upper level. The most useful FeXIII electron-density diagnostics in the SERTS spectral regions are assessed, in terms of the line pairs involved being (i) apparently free of atomic physics problems and blends, (ii) close in wavelength to reduce the effects of possible errors in the instrumental intensity calibration, and (iii) very sensitive to changes in Ne over the range 108-1011cm-3. It is concluded that the ratios which best satisfy these conditions are 200.03/202.04 and 203.17/202.04 for the 170-225 Å wavelength region, and 348.18/320.80, 348.18/368.16, 359.64/348.18 and 359.83/368.16 for 235-450 Å.

Extreme ultraviolet transitions of Fe XXI in solar, stellar and laboratory spectra

Recent R-matrix calculations of electron impact excitation rates for transitions among the 2s(2)2p(2), 2s2p(3) and 2p(4) levels of Fe XXI are used to derive theoretical electron density (N-e) sensitive emission-line ratios involving 2S2(2)p(2)-2s2p(3) transitions in the similar to 98-146 Angstrom wavelength range. A comparison of these with observations from the PLT tokamak plasma, for which the electron density has been independently determined, reveals generally very good agreement between theory and experiment, and in some instances removes discrepancies found previously. The observed Fe XXI ratios for a solar flare, obtained with the OSO-5 satellite, imply electron densities which are consistent, with discrepancies that do not exceed 0.2 dex. In addition, the derived values of N-e are similar to those estimated for the high-temperature regions of other solar flares. The good agreement between theory and observation, in particular for the tokamak spectra, provides experimental support for the accuracy of the present line-ratio calculations, and hence for the atomic data on which they are based.

Emission lines of [Cl II] in the optical spectra of gaseous nebulae

Recent R-matrix calculations of electron impact excitation rates among the 3s(2)3p(4) levels of Cl II are used to derive the nebular emission-line intensity ratios R-1=I(6161.8 Angstrom)/I(8578.7 Angstrom) and R-2=I(6161.8 Angstrom)/I(9123.6 Angstrom) as a function of electron temperature (T-e) and density (N-e). The ratios are found to be very sensitive to changes in T-e but not N-e for densities lower than 10(5) cm(-3). Hence, they should, in principle, provide excellent optical T-e diagnostics for planetary nebulae. The observed values of R-1 and R-2 for the planetary nebulae NGC 6741 and IC 5117, measured from spectra obtained with the Hamilton echelle spectrograph on the 3 m Shane Telescope, imply temperatures in excellent agreement with those derived from other diagnostic lines formed in the same region of the nebula as [Cl II]. This provides some observational support for the accuracy of the [Cl II] line ratio calculations and hence the atomic data on which they are based. The [Cl II] 8578.7 and 9123.6 Angstrom lines are identified for the first time (to our knowledge) in a high-resolution spectrum of the symbiotic star RR Telescopii, obtained with the University College London Echelle Spectrograph on the 3.9 m Anglo- Australian Telescope. However, the 6161.8 Angstrom feature is unfortunately too weak to be identified in the RR Telescopii observations, consistent with its predicted line strength.

SiIX emission lines in spectra obtained with the Solar EUV Research Telescope and Spectrograph (SERTS)

Theoretical electron-density-sensitive emission line ratios involving 2s(2)2p(2)-2s2p(3) transitions in Si IX between 223 and 350 Angstrom are presented. A comparison of these with an extensive dataset of solar-active-region, quiet-Sun, subflare and off-limb observations, obtained during rocket flights by the Solar EUV Research Telescope and Spectrograph (SERTS), reveals generally very good agreement between theory and experiment. This provides support for the accuracy of the line- ratio diagnostics, and hence the atomic data on which they are based. In particular, the density-sensitive intensity ratio I (258.10 Angstrom)/ I (349.87 Angstrom) offers an especially promising diagnostic for studies of coronal plasmas, as it involves two reasonably strong emission lines and varies by more than an order of magnitude over the useful density range of 10(9)-10(11) cm(-3). The 2s(2)2p(2) S-1(0) - 2s2p(3) P-1(1) transition at 259.77 Angstrom is very marginally identified for the first time in the SERTS database, although it has previously been detected in solar flare observations.

An investigation of Fe XV emission lines in solar flare spectra

Previously, large discrepancies have been found between theory and observation for Fe XV emission line ratios in solar flare spectra covering the 224-327 angstrom wavelength range, obtained by the Naval Research Laboratory's S082A instrument on board Skylab. These discrepancies have been attributed to either errors in the adopted atomic data or the presence of additional atomic processes not included in the modelling, such as fluorescence. However our analysis of these plus other S082A flare observations (the latter containing Fe XV transitions between 321-482 angstrom), performed using the most recent Fe XV atomic physics calculations in conjunction with a chianti synthetic flare spectrum, indicate that blending of the lines is primarily responsible for the discrepancies. As a result, most Fe XV lines cannot be employed as electron density diagnostics for solar flares, at least at the spectral resolution of S082A and similar instruments (i.e.similar to 0.1 angstrom). An exception is the intensity ratio I(3s3p P-3(2)-3p(2) P-3(1))/I(3s3p P-3(2)-3p(2) D-1(2))=I(321.8 angstrom)/I(327.0 angstrom), which appears to provide good estimates of the electron density at this spectral resolution.

Restricted rotation dynamics and far-infrared spectra of liquid water governed by elastic interactions

A semi-phenomenological model describing wideband dielectric and far-infrared spectra of liquid water was proposed recently by the same authors [J. Mol. Struct. 606 (2002) 9], where a small dipole-moment component changing harmonically with time determines a weak absorption band (termed here the R-band) centred at the wavenumber v similar to 200 cm(-1). In the present work, a rough molecular theory of the R-band based on the concept of elastic interactions is given. Stretching and bending of hydrogen bonds cause restricted rotation (RR) of a polar water molecule in terms of a dimer comprising the H- bonded molecules. Analytical expression for the RR frequency nu(str) is derived as a function of the RR amplitude, geometrical parameters and force constants. The density g(nu(str)) of frequency distribution is shown to be centred in the R-band. The spectrum of the dipolar auto-correlation function calculated for this structural-dynamical model is found. A composite model comprising two intermolecular potentials is proposed, which yields for water a good description of the experimental wideband (from 0 to 1000 cm(- 1)) spectra of complex permittivity and of absorption coefficient. The presented interpretation of these spectra is based on a concept that water presents a two-component solution, with components differing by the types of molecular rotation. (C) 2003 Elsevier B.V. All rights reserved.

Analytical calculation of far infrared spectra of ice in terms of a molecular model

Wideband far infrared (FIR) spectra of complex permittivity e(p) of ice are calculated in terms of a simple analytical theory based on the method of dipolar autocorrelation functions. The molecular model represents a revision of the model recently presented for liquid water in Adv. Chem. Phys. 127 (2003) 65. A composite two-fractional model is proposed. The model is characterised by three phenomenological potential wells corresponding to the three FIR bands observed in ice. The first fraction comprises dipoles reorienting in a rather narrow and deep hat-like well; these dipoles generate the librational band centred at the frequency approximate to 880 cm(-1). The second fraction comprises elastically interacting particles; they generate two nearby bands placed around frequency 200 cm(-1). For description of one of these bands the harmonic oscillator (HO) model is used, in which translational oscillations of two charged molecules along the H-bond are considered. The other band is produced by the H-bond stretch, which governs hindered rotation of a rigid dipole. Such a motion and its dielectric response are described in terms of a new cut parabolic (CP) model applicable for any vibration amplitude. The composite hat-HO-CP model results in a smooth epsilon(nu) ice spectrum, which does not resemble the noise-like spectra of ice met in the known literature. The proposed theory satisfactorily agrees with the experimental ice spectrum measured at - 7 degrees C. The calculated longitudinal optic-transverse optic (LO-TO) splitting occurring at approximate to 250 cm(-1) qualitatively agrees with the measured data. (c) 2004 Elsevier B.V. All rights reserved.

Specific and unspecific interactions in polar fluids in view of wideband dielectric far-infrared spectra

A simple molecular analytical theory of dielectric relaxation in strongly polar fluids is considered in terms of a semi- phenomenological approach. Theoretical spectra epsilon(v), a(v) of complex permittivity and absorption coefficient are fully determined by a form of intermolecular potential well, in which a dipole reorients. In a recent publication by VI. Gaiduk, O.F. Nielsen, and T.S. Perova [J. Molliq 95 (1002) 1-25] the wideband spectra of liquid H2O and D2O were described in terms of a composite model comprising the rectangular and the cosine squared potential wells. Much better results are achieved in this work, where the rectangular well is replaced by a well with a rounded bottom termed the hat-curved well. The spectrum of the auto-correlation function (ACF) is calculated for such a potential. The proposed theory of a composite model, comprising hat-curved and parabolic wells, is applied for liquid water. This model is capable for describing the Debye relaxation region, the second relaxation region in the submillimeter wavelength range, and the far infra-red (FIR) e(v), a(v) spectra, where an intense librational band and an additional weak band are placed, respectively, near 700 cm(-1) and 200 cm(-1). The latter band reflects the features of so-called specific (viz. directly related to H-bonds) interactions and the former band reflects the features of unspecific interactions. The physical mechanisms connected with these types of interactions are discussed in terms of two relevant types of water structure (types of molecular rotation). The proposed theory is also applied to a non-associated liquid in terms of one hat-curved potential well. (C) 2004 Elsevier B.V. All rights reserved.

Nonharmonic transverse vibration of the H-bonded molecules and the THz spectra in ice and water

A nonlinear equation of motion is found for the dimer comprising two charged H2O molecules. The THz dielectric response to nonharmonic vibration of a nonrigid dipole, forming the hydrogen bond (HB), is found in the direction transverse to this bond. An explicit expression is derived for the autocorrelator that governs the spectrum generated by transverse vibration (TV) of such a dipole. This expression is obtained by analytical solution of the truncated set of recurrence equations. The far infrared (FIR) spectra of ice at the temperature - 7 degrees C are calculated. The wideband, in the wavenumber (frequency) v range 0... 100.0 cm(-1), spectra are obtained for liquid water at room temperature and for supercooled water at -5.6 degrees C. All spectra are represented in terms of the complex permittivity epsilon(v) and the absorption coefficient alpha(v). The obtained analytical formula for epsilon comprises the term epsilon(perpendicular to) pertinent to the studied TV mechanism with three additional terms Delta epsilon(q), Delta epsilon(mu), and epsilon(or) arising, respectively, from: elastic harmonic vibration of charged molecules along the H-bond; elastic reorientation of HB permanent dipoles; and rather free libration of permanent dipoles in 'defects' of water/ice structure. The suggested TV-dielectric relaxation mechanism allows us: (a) to remove the THz 'deficit' of loss epsilon" inherent in previous theoretical studies; (b) to explain the THz loss and absorption spectra in supercooled (SC) water; and (c) to describe, in agreement with the experiment, the low- and high-frequency tails of the two bands of ice H2O located in the range 10...300 cm(-1). Specific THz dielectric properties of SC water are ascribed to association of water molecules, revealed in our study by transverse vibration of HB charged molecules. (C) 2006 Published by Elsevier B.V.