XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods

We have calculated XH-stretching (where X=O, C, F, Cl) fundamental and overtone transitions for three diatomics and a few small molecules using a local mode model. The potential energy curves and dipole moment functions are calculated using the recently developed explicitly correlated coupled cluster with single doubles and perturbative triples theory [CCSD_T_-F12] with the associated VXZ-F12 (where X=D, T, Q) basis sets. We find that the basis set convergence of calculated frequencies and oscillator strengths obtained with the explicitly correlated method is much more rapid than with conventional CCSD(T) and the Dunning type correlation consistent basis sets. Furthermore, CCSD(T)-F12 frequencies and oscillator strengths obtained with the VTZ-F12 and VQZ-F12 basis sets are found to be in excellent agreement with the CCSD(T) complete basis set limit. We find that comparison of CCSD(T)-F12 frequencies with experiment is less good. The inclusion of explicit correlation exposes the inherent error of the CCSD(T) method to overestimate vibrational frequencies, which is normally compensated by basis set incompleteness error. As a consequence, we suggest that conventional CCSD(T) in combination with the aug-cc-pVTZ or aug-cc-pVQZ basis sets is likely to yield calculated XH-stretching frequencies in closest agreement with experiment

Explicitly correlated intermolecular distances and interaction energies of hydrogen bonded complexes

We have optimized the lowest energy structures and calculated interaction energies for the H2O–H2O, H2O–H2S, H2O–NH3, and H2O–PH3 dimers with the recently developed explicitly correlated CCSD(T)-F12 methods and the associated VXZ-F12 (where X=D,T,Q) basis sets. For a given cardinal number, we find that the results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. In general we find that CCSD(T)-F12 results obtained with the VTZ-F12 basis set are better than the conventional CCSD(T) results obtained with an aug-cc-pV5Z basis set. We also investigate two ways to reduce the effects of basis set superposition error with conventional CCSD(T), namely, the popular counterpoise correction and limiting diffuse basis functions to the heavy atoms only. We find that for a given cardinal number, these selectively augmented correlation consistent basis sets yield results that are closer to the complete basis set limit than the corresponding fully augmented basis sets. Furthermore, we find that the difference between standard and counterpoise corrected interaction energies and intermolecular distances is reduced with the selectively augmented basis sets

Identification of the dimethylamine-trimethylamine complex in the gas phase

We have identified the dimethylamine-trimethylamine complex (DMA-TMA) at room temperature in the gas phase. The Fourier transform infrared (FTIR) spectrum of DMA-TMA in the NH-stretching fundamental region was obtained by spectral subtraction of spectra of each monomer. Explicitly correlated coupled cluster calculations were used to determine the minimum energy structure and interaction energy of DMA-TMA. Frequencies and intensities of NH-stretching transitions were also calculated at this level of theory with an anharmonic oscillator local mode model. The fundamental NH-stretching intensity in DMA-TMA is calculated to be approximately 700 times larger than that of the DMA monomer. The measured and calculated intensity is used to determine a room temperature equilibrium constant of DMA-TMA of 1.7 × 10⁻³ atm⁻¹ at 298 K

The evolution of the galactic morphological types in clusters

The morphological types of galaxies in nine clusters in the redshift range 0.1<z<0.25 are derived from very good seeing images taken at the NOT and the La Silla Danish telescopes. With the purpose of investigating the evolution of the fraction of different morphological types with redshift, we compare our results with the morphological content of nine distant clusters studied by the MORPHS group, five clusters observed with HST-WFPC2 at redshift z = 0.2-0.3, and Dressler's (1980) large sample of nearby clusters. After having checked the reliability of our morphological classification both in an absolute sense and relative to the MORPHS scheme, we analyze the relative occurrence of elliptical, S0 and spiral galaxies as a function of the cluster properties and redshift. We find a large intrinsic scatter in the S0/E ratio, mostly related to the cluster morphology. In particular, in our cluster sample, clusters with a high concentration of ellipticals display a low S0/E ratio and, vice-versa, low concentration clusters have a high S0/E. At the same time, the trend of the morphological fractions and ratios with redshift clearly points to a morphological evolution: as the redshift decreases, the S0 population tends to grow at the expense of the spiral population, whereas the frequency of Es remains almost constant. We also analyze the morphology-density (MD) relation in our clusters and find that -similarly to higher redshift clusters- a good MD relation exists in the high-concentration clusters, while it is absent in the less concentrated clusters. Finally, the comparison of the MD relation in our clusters with that of the D97 sample suggests that the transformation of spirals into S0 galaxies becomes more efficient with decreasing local density.Comment: 24 pages including 11 figures and 4 tables, accepted for publication in Ap

Isoprene photooxidation : new insights into the production of acids and organic nitrates

We describe a nearly explicit chemical mechanism for isoprene photooxidation guided by chamber studies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the total isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chemistry of the δ-hydroxy channel with less than 5% of the carbon following the trans branch. The modelled yield of isoprene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NOx. Methacrolein nitrates (modelled yield ≃15±3% from methacrolein) and methylvinylketone nitrates (modelled yield ≃11±3% yield from methylvinylketone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived nitrate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summarized in a condensed scheme appropriate for use in global chemical transport models

Calculated two-photon electronic transitions in sulfuric acid and its atmospheric relevance

Non Peer reviewe

Superconducting, Insulating, and Anomalous Metallic Regimes in a Gated Two-Dimensional Semiconductor-Superconductor Array

The superconductor-insulator transition in two dimensions has been widely investigated as a paradigmatic quantum phase transition. The topic remains controversial, however, because many experiments exhibit a metallic regime with saturating low-temperature resistance, at odds with conventional theory. Here, we explore this transition in a novel, highly controllable system, a semiconductor heterostructure with epitaxial Al, patterned to form a regular array of superconducting islands connected by a gateable quantum well. Spanning nine orders of magnitude in resistance, the system exhibits regimes of superconducting, metallic, and insulating behavior, along with signatures of flux commensurability and vortex penetration. An in-plane magnetic field eliminates the metallic regime, restoring the direct superconductor-insulator transition, and improves scaling, while strongly altering the scaling exponent

Identification of OSSO as a near-UV absorber in the Venusian atmosphere

The planet Venus exhibits atmospheric absorption in the 320–400 nm wavelength range produced by unknown chemistry. We investigate electronic transitions in molecules that may exist in the atmosphere of Venus. We identify two different S_2O_2 isomers, cis-OSSO and trans-OSSO, which are formed in significant amounts and are removed predominantly by near-UV photolysis. We estimate the rate of photolysis of cis- and trans-OSSO in the Venusian atmosphere and find that they are good candidates to explain the enigmatic 320–400 nm near-UV absorption. Between 58 and 70 km, the calculated OSSO concentrations are similar to those of sulfur monoxide (SO), generally thought to be the second most abundant sulfur oxide on Venus

The WINGS Survey: a progress report

A two-band (B and V) wide-field imaging survey of a complete, all-sky X-ray selected sample of 78 clusters in the redshift range z=0.04-0.07 is presented. The aim of this survey is to provide the astronomical community with a complete set of homogeneous, CCD-based surface photometry and morphological data of nearby cluster galaxies located within 1.5 Mpc from the cluster center. The data collection has been completed in seven observing runs at the INT and ESO-2.2m telescopes. For each cluster, photometric data of about 2500 galaxies (down to V~23) and detailed morphological information of about 600 galaxies (down to V~21) are obtained by using specially designed automatic tools. As a natural follow up of the photometric survey, we also illustrate a long term spectroscopic program we are carrying out with the WHT-WYFFOS and AAT-2dF multifiber spectrographs. Star formation rates and histories, as well as metallicity estimates will be derived for about 350 galaxies per cluster from the line indices and equivalent widths measurements, allowing us to explore the link between the spectral properties and the morphological evolution in high- to low-density environments, and across a wide range in cluster X-ray luminosities and optical properties.Comment: 12 pages, 10 eps figures, Proceedings of the SAIt Conference 200

Infrared and Near-Infrared Spectroscopy of Acetylacetone and Hexafluoroacetylacetone

The infrared and near-infrared spectra of acetylacetone, acetylacetone-d8, and hexafluoroacetylacetone are characterized from experiment and computations at different levels. In the fundamental region, the intramolecular hydrogen bonded OH-stretching transition is clearly observed as a very broad band with substantial structure and located at significantly lower frequency compared to common OH-stretching frequencies. There is no clear evidence for OH-stretching overtone transitions in the near-infrared region, which is dominated by the CH-stretching overtones of the methine and methyl CH bonds. From molecular dynamics (MD) simulations, with a potential energy surface previously validated for tunneling splittings, the infrared spectra are determined and used in assigning the experimentally measured ones. It is found that the simulated spectrum in the region associated with the proton transfer mode is exquisitely sensitive to the height of the barrier for proton transfer. Comparison of the experimental and the MD simulated spectra establishes that the barrier height is around 2.5 kcal/mol, which favorably compares with 3.2 kcal/mol obtained from high-level electronic structure calculations