ARE AB INITIO QUANTUM CHEMISTRY METHODS ABLE TO PREDICT VIBRATIONAL STATES UP TO THE DISSOCIATION LIMIT FOR MULTI-ELECTRON MOLECULES CLOSE TO SPECTROSCOPIC ACCURACY?

Author Institution: Eotvos Lorand University, Budapest, Hungary; Slovak University of Technology, Trnava, Slovak Republic; Reims University, Reims, FranceThe aim of the study was to explore the limits of initio methods towards the description of excited vibrational levels up to the dissociation limit for molecules having more than two electrons. To this end a high level {\it ab initio} potential energy function was constructed for the four-electron LiH molecule in order to accurately predict a complete set of bound vibrational levels corresponding to the electronic ground state. It was composed from: a) an {\it ab initio} non-relativistic potential obtained at the MR-CISD level including size-extensivity corrections and quintuple-sextuple $\zeta$ extrapolation of the basis, b) MVD (Mass-velocity-Darwin) relativistic corrections obtained at icMR-CISD/cc-pwCV5Z level, and c) DBOC (Diagonal Born-Oppenheimer correction) obtained at the MR-CISD/cc-pwCVTZ level. Finally, the importance of non-adiabatic effects was also tested by using atomic masses in the vibrational kinetic energy operator and by calculation of non-adiabatic coupling by {\it ab initio} methods. The calculated vibrational levels were compared with those obtained from experimental data [J.A. Coxon and C.S. Dickinson, \textit{J. Chem. Phys.}, 2004, \textbf{121}, 9378]. Our best estimate of the potential curve results in vibrational energies with a RMS deviation of only $\sim$1 \wn\ for the entire set of all empirically determined vibrational levels known so far. These results represent a drastic improvement over previous theoretical predictions of vibrational levels of $^7$LiH up to dissociation, $D_0$, which was predicted to be 19594 cm$^{-1}$. In addition, rotational levels have also been calculated. The RMS deviation between our ab initio calculations and empirical results by Coxon and Dickinson for rotational spacings $\Delta E = E(v, J = 1)-E(v, J = 0)$ over all available vibrational states of $^7$LiH from $v = 0$ to $v= 20$ is 0.010 \wn\ (with nuclear masses) and 0.006 \wn\ (with atomic masses). Note that for high vibrational states with $v > 6$ this falls within the uncertainty of the measurements

The Generality of the GUGA MRCI Approach in COLUMBUS for Treating Complex Quantum Chemistry

The core part of the program system COLUMBUS allows highly efficient calculations using variational multireference (MR) methods in the framework of configuration interaction with single and double excitations (MR-CISD) and averaged quadratic coupled-cluster calcu- lations (MR-AQCC), based on uncontracted sets of configurations and the graphical unitary group approach (GUGA). The availability of analytic MR-CISD and MR-AQCC energy gradients and analytic nonadiabatic couplings for MR-CISD enables exciting applications including, e.g., investigations of π-conjugated biradicaloid compounds, calculations of multitudes of excited states, development of dia- batization procedures, and furnishing the electronic structure information for on-the-fly surface nonadiabatic dynamics. With fully vari- ational uncontracted spin-orbit MRCI, COLUMBUS provides a unique possibility of performing high-level calculations on compounds containing heavy atoms up to lanthanides and actinides. Crucial for carrying out all of these calculations effectively is the availability of an efficient parallel code for the CI step. Configuration spaces of several billion in size now can be treated quite routinely on stan- dard parallel computer clusters. Emerging developments in COLUMBUS, including the all configuration mean energy multiconfiguration self-consistent field method and the graphically contracted function method, promise to allow practically unlimited configuration space dimensions. Spin density based on the GUGA approach, analytic spin-orbit energy gradients, possibilities for local electron correlation MR calculations, development of general interfaces for nonadiabatic dynamics, and MRCI linear vibronic coupling models conclude this overview

Ongoing Formation of Bulges and Black Holes in the Local Universe: New Insights from GALEX

We analyze a volume-limited sample of massive bulge-dominated galaxies with data from both the Sloan Digital Sky Survey and the Galaxy Evolution Explorer (GALEX) satellite. The galaxies have central velocity dispersions greater than 100 km/s and stellar surface mass densities that lie above the value where galaxies transition from actively star forming to passive systems. The sample is limited to redshifts 0.03<z<0.07. At these distances, the SDSS spectra sample the light from the bulge-dominated central regions of the galaxies. The GALEX NUV data provide high sensitivity to low rates of global star formation in these systems. Our sample of bulge-dominated galaxies exhibits a much larger dispersion in NUV-r colour than in optical g-r colour. Nearly all of the galaxies with bluer NUV-r colours are AGN. Both GALEX images and SDSS colour profiles demonstrate that the excess UV light is associated with an extended disk. We find that galaxies with red outer regions almost never have a young bulge or a strong AGN. Galaxies with blue outer regions have bulges and black holes that span a wide range in age and accretion rate. Galaxies with young bulges and strongly accreting black holes almost always have blue outer disks. Our suggested scenario is one in which the source of gas that builds the bulge and black hole is a low mass reservoir of cold gas in the disk.The presence of this gas is a necessary, but not sufficient condition for bulge and black hole growth. Some mechanism must transport this gas inwards in a time variable way. As the gas in the disk is converted into stars, the galaxies will turn red, but further gas infall can bring them back into the blue NUV-r sequence.(Abridged)Comment: 34 pages, 16 figures. Accepted for the GALEX special issue of ApJ

Multireference approaches for excited states of molecules

Understanding the properties of electronically excited states is a challenging task that becomes increasingly important for numerous applications in chemistry, molecular physics, molecular biology, and materials science. A substantial impact is exerted by the fascinating progress in time-resolved spectroscopy, which leads to a strongly growing demand for theoretical methods to describe the characteristic features of excited states accurately. Whereas for electronic ground state problems of stable molecules the quantum chemical methodology is now so well developed that informed nonexperts can use it efficiently, the situation is entirely different concerning the investigation of excited states. This review is devoted to a specific class of approaches, usually denoted as multireference (MR) methods, the generality of which is needed for solving many spectroscopic or photodynamical problems. However, the understanding and proper application of these MR methods is often found to be difficult due to their complexity and their computational cost. The purpose of this review is to provide an overview of the most important facts about the different theoretical approaches available and to present by means of a collection of characteristic examples useful information, which can guide the reader in performing their own applications

The UV-Optical Galaxy Color-Magnitude Diagram. I. Basic Properties

We have analyzed the bivariate distribution of galaxies as a function of ultraviolet-optical colors and absolute magnitudes in the local universe. The sample consists of galaxies with redshifts and optical photometry from the Sloan Digital Sky Survey (SDSS) main galaxy sample matched with detections in the near-ultraviolet (NUV) and far-ultraviolet (FUV) bands in the Medium Imaging Survey being carried out by the Galaxy Evolution Explorer (GALEX) satellite. In the (NUV − r)_(0.1) versus M_(r,0.1) galaxy color-magnitude diagram, the galaxies separate into two well-defined blue and red sequences. The (NUV − r)_(0.1) color distribution at each M_(r,0.1) is not well fit by the sum of two Gaussians due to an excess of galaxies in between the two sequences. The peaks of both sequences become redder with increasing luminosity, with a distinct blue peak visible up to M_(r,0.1) ~ − 23. The r_(0.1)-band luminosity functions vary systematically with color, with the faint-end slope and characteristic luminosity gradually increasing with color. After correcting for attenuation due to dust, we find that approximately one-quarter of the color variation along the blue sequence is due to dust, with the remainder due to star formation history and metallicity. Finally, we present the distribution of galaxies as a function of specific star formation rate and stellar mass. The specific star formation rates imply that galaxies along the blue sequence progress from low-mass galaxies with star formation rates that increase somewhat with time to more massive galaxies with a more or less constant star formation rate. Above a stellar mass of ~10^(10.5) M_☉, galaxies with low ratios of current to past averaged star formation rate begin to dominate

The Calibration and Data Products of the Galaxy Evolution Explorer

We describe the calibration status and data products pertaining to the GR2 and GR3 data releases of the Galaxy Evolution Explorer (GALEX). These releases have identical pipeline calibrations that are significantly improved over the GR1 data release. GALEX continues to survey the sky in the Far Ultraviolet (FUV, ~154 nm) and Near Ultraviolet (NUV, ~232 nm) bands, providing simultaneous imaging with a pair of photon counting, microchannel plate, delay line readout detectors. These 1.25 degree field-of-view detectors are well-suited to ultraviolet observations because of their excellent red rejection and negligible background. A dithered mode of observing and photon list output pose complex requirements on the data processing pipeline, entangling detector calibrations and aspect reconstruction algorithms. Recent improvements have achieved photometric repeatability of 0.05 and 0.03 mAB in the FUV and NUV, respectively. We have detected a long term drift of order 1% FUV and 6% NUV over the mission. Astrometric precision is of order 0.5" RMS in both bands. In this paper we provide the GALEX user with a broad overview of the calibration issues likely to be confronted in the current release. Improvements are likely as the GALEX mission continues into an extended phase with a healthy instrument, no consumables, and increased opportunities for guest investigations.Comment: Accepted to the ApJS (a special GALEX issue