Calculations of rovibrational energies and dipole transition intensities for polyatomic molecules using MULTIMODE

We report rigorous calculations of rovibrational energies and dipole transition intensities for three molecules using a new version of the code MULTIMODE. The key features of this code which permit, for the first time, such calculations for moderately sized but otherwise general polyatomic molecules are briefly described. Calculations for the triatomic molecule BF(2) are done to validate the code. New calculations for H(2)CO and H(2)CS are reported; these make use of semiempirical potentials but ab initio dipole moment surfaces. The new dipole surface for H(2)CO is a full-dimensional fit to the dipole moment obtained with the coupled-cluster with single and double excitations and a perturbative treatment of triple excitations method with the augmented correlation consistent triple zeta basis set. Detailed comparisons are made with experimental results from a fit to relative data for H(2)CS and absolute intensities from the HITRAN database for H(2)CO.

Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Theoretical calculation of absorption intensities of C2H and C2D

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98,1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C2H radical and its deuterated isotopomer for energies up to 10000 cm(-1) above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molee. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.

Ab initio prediction of the infrared-absorption spectrum of the C2Cl radical

The three lowest (1(2)A('), 2(2)A('), and 1(2)A(')) potential-energy surfaces of the C2Cl radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio using a large basis set and multireference configuration-interaction techniques. The electronic ground state is confirmed to be bent with a very low barrier to linearity, due to the strong nonadiabatic electronic interactions taking place in this system. The rovibronic energy levels of the (CCCl)-C-12-C-12-Cl-35 isotopomer and the absolute absorption intensities at a temperature of 5 K have been calculated, to an upper limit of 2000 cm(-1), using diabatic potential-energy and dipole moment surfaces and a recently developed variational method. The resulting vibronic states arise from a strong mixture of all the three electronic components and their assignments are intrinsically ambiguous. (c) 2005 American Institute of Physics.

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

Perceptual compensation for reverberation in speech identification: effects of single-band, multiple-band and wideband noise contexts

Perceptual effects of room reverberation on a "sir" or "stir" test-word can be observed when the level of reverberation in the word is increased, while the reverberation in a surrounding 'context I utterance remains at a minimal level. The result is that listeners make more "sit" identifications. When the context's reverberation is also increased, to approach the level in the test word, extrinsic perceptual compensation is observed, so that the number of listeners' "sir" identifications reduces to a value similar to that found with minimal reverberation. Thus far, compensation effects have only been observed with speech or speech-like contexts in which the short-term spectrum changes as the speaker's articulators move. The results reported here show that some noise contexts with static short-term spectra can also give rise to compensation. From these experiments it would appear that compensation requires a context with a temporal envelope that fluctuates to some extent, so that parts of it resemble offsets. These findings are consistent with a rather general kind of perceptual compensation mechanism; one that is informed by the 'tails' that reverberation adds at offsets. Other results reported here show that narrow-band contexts do not bring about compensation, even when their temporal-envelopes are the same as those of the more effective wideband contexts. These results suggest that compensation is confined to the frequency range occupied by the context, and that in a wideband sound it might operate in a 'band by band' manner.

Room reflections and constancy in speech-like sounds: within-band effects

The experiment asks whether constancy in hearing precedes or follows grouping. Listeners heard speech-like sounds comprising 8 auditory-filter shaped noise-bands that had temporal envelopes corresponding to those arising in these filters when a speech message is played. The „context‟ words in the message were “next you‟ll get _to click on”, into which a “sir” or “stir” test word was inserted. These test words were from an 11-step continuum that was formed by amplitude modulation. Listeners identified the test words appropriately and quite consistently, even though they had the „robotic‟ quality typical of this type of 8-band speech. The speech-like effects of these sounds appears to be a consequence of auditory grouping. Constancy was assessed by comparing the influence of room reflections on the test word across conditions where the context had either the same level of reflections, or where it had a much lower level. Constancy effects were obtained with these 8-band sounds, but only in „matched‟ conditions, where the room reflections were in the same bands in both the context and the test word. This was not the case in a comparison „mismatched‟ condition, and here, no constancy effects were found. It would appear that this type of constancy in hearing precedes the across-channel grouping whose effects are so apparent in these sounds. This result is discussed in terms of the ubiquity of grouping across different levels of representation.

Perceptual constancy, reverberation, and grouping: within-band effects

Perceptual constancy effects are observed when differing amounts of reverberation are applied to a context sentence and a test‐word embedded in it. Adding reverberation to members of a “sir”‐“stir” test‐word continuum causes temporal‐envelope distortion, which has the effect of eliciting more sir responses from listeners. If the same amount of reverberation is also applied to the context sentence, the number of sir responses decreases again, indicating an “extrinsic” compensation for the effects of reverberation. Such a mechanism would effect perceptual constancy of phonetic perception when temporal envelopes vary in reverberation. This experiment asks whether such effects precede or follow grouping. Eight auditory‐filter shaped noise‐bands were modulated with the temporal envelopes that arise when speech is played through these filters. The resulting “gestalt” percept is the appropriate speech rather than the sound of noise‐bands, presumably due to across‐channel “grouping.” These sounds were played to listeners in “matched” conditions, where reverberation was present in the same bands in both context and test‐word, and in “mismatched” conditions, where the bands in which reverberation was added differed between context and test‐word. Constancy effects were obtained in matched conditions, but not in mismatched conditions, indicating that this type of constancy in hearing precedes across‐channel grouping.

A molecular T-matrix approach to calculating low-energy electron diffusion intensities for ordered molecular adsorbates

We present a novel approach to calculating Low-Energy Electron Diffraction (LEED) intensities for ordered molecular adsorbates. First, the intra-molecular multiple scattering is computed to obtain a non-diagonal molecular T-matrix. This is then used to represent the entire molecule as a single scattering object in a conventional LEED calculation, where the Layer Doubling technique is applied to assemble the different layers, including the molecular ones. A detailed comparison with conventional layer-type LEED calculations is provided to ascertain the accuracy of this scheme of calculation. Advantages of this scheme for problems involving ordered arrays of molecules adsorbed on surfaces are discussed.

Unusually high differential attenuation at C band: Results from a two-year analysis of the French Trappes polarimetric radar data

The differential phase (ΦDP) measured by polarimetric radars is recognized to be a very good indicator of the path integrated by rain. Moreover, if a linear relationship is assumed between the specific differential phase (KDP) and the specific attenuation (AH) and specific differential attenuation (ADP), then attenuation can easily be corrected. The coefficients of proportionality, γH and γDP, are, however, known to be dependent in rain upon drop temperature, drop shapes, drop size distribution, and the presence of large drops causing Mie scattering. In this paper, the authors extensively apply a physically based method, often referred to as the “Smyth and Illingworth constraint,” which uses the constraint that the value of the differential reflectivity ZDR on the far side of the storm should be low to retrieve the γDP coefficient. More than 30 convective episodes observed by the French operational C-band polarimetric Trappes radar during two summers (2005 and 2006) are used to document the variability of γDP with respect to the intrinsic three-dimensional characteristics of the attenuating cells. The Smyth and Illingworth constraint could be applied to only 20% of all attenuated rays of the 2-yr dataset so it cannot be considered the unique solution for attenuation correction in an operational setting but is useful for characterizing the properties of the strongly attenuating cells. The range of variation of γDP is shown to be extremely large, with minimal, maximal, and mean values being, respectively, equal to 0.01, 0.11, and 0.025 dB °−1. Coefficient γDP appears to be almost linearly correlated with the horizontal reflectivity (ZH), differential reflectivity (ZDR), and specific differential phase (KDP) and correlation coefficient (ρHV) of the attenuating cells. The temperature effect is negligible with respect to that of the microphysical properties of the attenuating cells. Unusually large values of γDP, above 0.06 dB °−1, often referred to as “hot spots,” are reported for 15%—a nonnegligible figure—of the rays presenting a significant total differential phase shift (ΔϕDP > 30°). The corresponding strongly attenuating cells are shown to have extremely high ZDR (above 4 dB) and ZH (above 55 dBZ), very low ρHV (below 0.94), and high KDP (above 4° km−1). Analysis of 4 yr of observed raindrop spectra does not reproduce such low values of ρHV, suggesting that (wet) ice is likely to be present in the precipitation medium and responsible for the attenuation and high phase shifts. Furthermore, if melting ice is responsible for the high phase shifts, this suggests that KDP may not be uniquely related to rainfall rate but can result from the presence of wet ice. This hypothesis is supported by the analysis of the vertical profiles of horizontal reflectivity and the values of conventional probability of hail indexes.

Evaluation of two "integrated" polarimetric Quantitative Precipitation Estimation (QPE) algorithms at C-band

Two so-called “integrated” polarimetric rate estimation techniques, ZPHI (Testud et al., 2000) and ZZDR (Illingworth and Thompson, 2005), are evaluated using 12 episodes of the year 2005 observed by the French C-band operational Trappes radar, located near Paris. The term “integrated” means that the concentration parameter of the drop size distribution is assumed to be constant over some area and the algorithms retrieve it using the polarimetric variables in that area. The evaluation is carried out in ideal conditions (no partial beam blocking, no ground-clutter contamination, no bright band contamination, a posteriori calibration of the radar variables ZH and ZDR) using hourly rain gauges located at distances less than 60 km from the radar. Also included in the comparison, for the sake of benchmarking, is a conventional Z = 282R1.66 estimator, with and without attenuation correction and with and without adjustment by rain gauges as currently done operationally at Météo France. Under those ideal conditions, the two polarimetric algorithms, which rely solely on radar data, appear to perform as well if not better, pending on the measurements conditions (attenuation, rain rates, …), than the conventional algorithms, even when the latter take into account rain gauges through the adjustment scheme. ZZDR with attenuation correction is the best estimator for hourly rain gauge accumulations lower than 5 mm h−1 and ZPHI is the best one above that threshold. A perturbation analysis has been conducted to assess the sensitivity of the various estimators with respect to biases on ZH and ZDR, taking into account the typical accuracy and stability that can be reasonably achieved with modern operational radars these days (1 dB on ZH and 0.2 dB on ZDR). A +1 dB positive bias on ZH (radar too hot) results in a +14% overestimation of the rain rate with the conventional estimator used in this study (Z = 282R^1.66), a -19% underestimation with ZPHI and a +23% overestimation with ZZDR. Additionally, a +0.2 dB positive bias on ZDR results in a typical rain rate under- estimation of 15% by ZZDR.

Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800–12,000 cm−1 under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800–12,000 cm−1 spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000–9200 cm−1 spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000–9200 cm−1 spectral region) are used. This strongly suggests that the H2O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m−2 when using either the UCL08 or Oudot line parameters in the 8000–9200 cm−1 region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500–2900 cm−1 region in the observations.

Building a tropical-extratropical cloud band metbot

An automated cloud band identification procedure is developed that captures the meteorology of such events over southern Africa. This “metbot” is built upon a connected component labelling method that enables blob detection in various atmospheric fields. Outgoing longwave radiation is used to flag candidate cloud band days by thresholding the data and requiring detected blobs to have sufficient latitudinal extent and exhibit positive tilt. The Laplacian operator is used on gridded reanalysis variables to highlight other features of meteorological interest. The ability of this methodology to capture the significant meteorology and rainfall of these synoptic systems is tested in a case study. Usefulness of the metbot in understanding event to event similarities of meteorological features is demonstrated, highlighting features previous studies have noted as key ingredients to cloud band development in the region. Moreover, this allows the presentation of a composite cloud band life cycle for southern Africa events. The potential of metbot to study multiscale interactions is discussed, emphasising its key strength: the ability to retain details of extreme and infrequent events. It automatically builds a database that is ideal for research questions focused on the influence of intraseasonal to interannual variability processes on synoptic events. Application of the method to convergence zone studies and atmospheric river descriptions is suggested. In conclusion, a relation-building metbot can retain details that are often lost with object-based methods but are crucial in case studies. Capturing and summarising these details may be necessary to develop deeper process-level understanding of multiscale interactions.