Shallow Potential Wells Research Articles

Low-lying electronic states of LiF molecule with inner electrons correlation

The potential energy curves and dipole moments of the low-lying electronic states of LiF molecule are performed by using highly accurate multi-reference configuration interaction with Awcv5z basis sets. 1s, the inner shell of Li is considered as the closed orbit, which is used to characterise the spectroscopic properties of a manifold of singlet and triplet states. 16 electronic states correlate with two lowest dissociation channels Li(2S)+F(2P) and Li(2P)+F(2P) are investigated. Spectroscopic parameters of the ground state X1Σ+ have been evaluated and critically compared with the available experimental values and the other theoretical data. However, spectroscopic parameters of 13Π, 11Δ, 11Σ−, 11Π, 13Σ+, 23Σ+, 13Δ, 13Σ−, 23Π, 21Π, 33Π, 31Π and 33Σ+ states are studied for the first time. These 13 excited states have shallow potential wells, and the dispersion coefficients of these excited states are predicted. In additional, oscillator strengths of excited states at equilibrium distances are also predicted.

Degenerate nucleophilic substitution in phosphonium salts.

Rates and energy barriers of degenerate halide substitution on tetracoordinate halophosphonium cations have been measured by NMR techniques (VT and EXSY) using a novel experimental design whereby a chiral substituent ((s)Bu) lifts the degeneracy of the resultant salts. Concomitantly, a viable computational approach to the system was developed to gain mechanistic insights into the structure and relative stabilities of the species involved. Both approaches strongly suggest a two-step mechanism of formation of a pentacoordinate dihalophosphorane via backside attack followed by dissociation, resulting in inversion of configuration at phosphorus. The experimentally determined barriers range from <9 kcal mol(-1) to nearly 20 kcal mol(-1), ruling out a mechansm via Berry pseudorotation involving equatorial halides. In all cases studied, epimerization of chlorophosphonium chlorides has a lower energy barrier (by 2 kcal mol(-1)) than the analogous bromo salts. Calculations determined that this was due to the easier accessibility in solution of pentacoordinate dichlorophosphoranes when compared to analogous dibromophosphoranes. In line with the proposed associative mechanism, bulky substituents slow the reaction in the order Me < Et < (i)Pr < (t)Bu. Bulky substituents affect the shape of the reaction energy profile so that the pentacoordinate intermediate is destabilized eventually becoming a transition state. The magnitude of the steric effects is comparable to that of the same substituents on substitution at primary alkyl halides, which can be rationalized by the relatively longer P-C bonds. The reaction displays first-order kinetics due to the prevalence of tight- or solvent-separated ion pairs in solution. Three-dimensional reaction potential energy profiles (More O'Ferrall-Jencks plots) indicated a relatively shallow potential well corresponding to the trigonal bipyramid intermediate flanked by two transition states.

Nonstatistical dynamics on the caldera.

We explore both classical and quantum dynamics of a model potential exhibiting a caldera: that is, a shallow potential well with two pairs of symmetry related index one saddles associated with entrance/exit channels. Classical trajectory simulations at several different energies confirm the existence of the "dynamical matching" phenomenon originally proposed by Carpenter, where the momentum direction associated with an incoming trajectory initiated at a high energy saddle point determines to a considerable extent the outcome of the reaction (passage through the diametrically opposing exit channel). By studying a "stretched" version of the caldera model, we have uncovered a generalized dynamical matching: bundles of trajectories can reflect off a hard potential wall so as to end up exiting predominantly through the transition state opposite the reflection point. We also investigate the effects of dissipation on the classical dynamics. In addition to classical trajectory studies, we examine the dynamics of quantum wave packets on the caldera potential (stretched and unstretched). These computations reveal a quantum mechanical analogue of the "dynamical matching" phenomenon, where the initial expectation value of the momentum direction for the wave packet determines the exit channel through which most of the probability density passes to product.

Size matters! On the way to ionic liquid systems without ion pairing.

Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium-sized [NTf2 ](-) (0.230 nm(3) ; Tf=CF3 SO3 (-) ) and the large [Al(hfip)4 ](-) (0.581 nm(3) ; hfip=OC(H)(CF3 )2 ) anions were synthesized and characterized. Their temperature-dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel-Fulcher-Tammann (VFT) behavior. Ion-specific self-diffusion constants were measured at room temperature by pulsed-gradient stimulated-echo (PGSTE) NMR experiments. In general, self-diffusion constants of both cations and anions in [Al(hfip)4 ](-) -based ILs were higher than in [NTf2 ](-) -based ILs. Ionicities were calculated from self-diffusion constants and measured bulk conductivities, and showed that [Al(hfip)4 ](-) -based ILs yield higher ionicities than their [NTf2 ](-) analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)4 ](-) -based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)4 ](-) . Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions.

The bias of DLAs at z∼2.3: evidence for very strong stellar feedback in shallow potential wells

We discuss the recent Baryon Oscillation Spectroscopic Survey measurement of a rather high bias factor for the host galaxies/haloes of Damped Lyman-alpha Absorbers (DLAs), in the context of our previous modelling of the physical properties of DLAs within the $\Lambda$ cold dark matter paradigm. Joint modelling of the column density distribution, the velocity width distribution of associated low ionization metal absorption, and the bias parameter suggests that DLAs are hosted by galaxies with dark matter halo masses in the range $10 < \log M_v < 12$, with a rather sharp cutoff at the lower mass end, corresponding to virial velocities of 35 km/sec. The observed properties of DLAs appear to suggest efficient (stellar) feedback in haloes with masses/virial velocities below the cutoff and a large retained baryon fraction (> 35 %) in haloes above the cutoff.

THE STELLAR HALOS OF MASSIVE ELLIPTICAL GALAXIES. II. DETAILED ABUNDANCE RATIOS AT LARGE RADIUS

We study the radial dependence in stellar populations of 33 nearby early-type galaxies with central stellar velocity dispersions sigma* > 150 km/s. We measure stellar population properties in composite spectra, and use ratios of these composites to highlight the largest spectral changes as a function of radius. Based on stellar population modeling, the typical star at 2 R_e is old (~10 Gyr), relatively metal poor ([Fe/H] -0.5), and alpha-enhanced ([Mg/Fe]~0.3). The stars were made rapidly at z~1.5-2 in shallow potential wells. Declining radial gradients in [C/Fe], which follow [Fe/H], also arise from rapid star formation timescales due to declining carbon yields from low-metallicity massive stars. In contrast, [N/Fe] remains high at large radius. Stars at large radius have different abundance ratio patterns from stars in the center of any present-day galaxy, but are similar to Milky Way thick disk stars. Our observations are thus consistent with a picture in which the stellar outskirts are built up through minor mergers with disky galaxies whose star formation is truncated early (z~1.5-2).

How does radiative feedback from an ultraviolet background impact reionization?

An ionizing UV background (UVB) inhibits gas accretion and photo-evaporates gas from the shallow potential wells of small, dwarf galaxies. During cosmological reionization, this effect can result in negative feedback: suppressing star-formation inside HII regions, thus impeding their continued growth. It is difficult to model this process, given the enormous range of scales involved. We tackle this problem using a tiered approach: combining parameterized results from single-halo collapse simulations with large-scale models of reionization. In the resulting reionization models, the ionizing emissivity of galaxies depends on the local values of the reionization redshift and the UVB intensity. We present a physically-motivated analytic expression for the average minimum mass of star-forming galaxies, which can be readily used in modeling galaxy formation. We find that UVB feedback: (i) delays the end stages of reionization by less than 0.5 in redshift; (ii) results in a more uniform distribution of HII regions, peaked on smaller-scales (with large-scale ionization power suppressed by tens of percent); and (iii) suppresses the global photoionization rate per baryon by a factor of < 2 towards the end of reionization. However, the impact is modest, since the hydrodynamic response of the gas to the UVB occurs on a time-scale comparable to reionization. In particular, the popular approach of modeling UVB feedback with an instantaneous transition in the minimum mass of star-forming galaxies, dramatically overestimates its importance. UVB feedback does not significantly affect reionization unless: (i) molecularly-cooled galaxies contribute significantly to reionization; or (ii) internal feedback processes strongly couple with UVB feedback in the early Universe. Since both are considered unlikely, we conclude that there is no significant self-regulation of reionization by UVB feedback.

Quantization rule for highly excited vibrational states of H

We analyse the influence of the attractive tail of the p–H two-body potential on the energy progression of the near-threshold rotationless bound states of the H molecular ion. For the 1sσ g configuration we study different definitions of the reference potential describing the potential tail. In each case, the scattering length consistent with the energies of the highly excited vibrational states, as calculated by Hilico et al. [Eur. Phys. J. D 12, 449 (2000)], is found to lie in the range between −30.5 and −31 au. In the 2pσ u configuration, for which there is an extremely weakly bound v = 1 vibrational state [Carbonell et al., Europhys. Lett. 64, 316 (2003)], we obtain a scattering length near 762.8 au. In contrast to previously conveyed impressions, the weakly bound v = 1 state can be satisfactorily described as the excited state in a distant shallow potential well of the p–H two-body potential, provided that a sufficient number of terms is included in the representation of the large-distance behaviour of this potential.

The fate of heavy elements in dwarf galaxies – the role of mass and geometry

Energetic feedback from Supernovae and stellar winds can drive galactic winds. Dwarf galaxies, due to their shallower potential wells, are assumed to be more vulnerable to this phenomenon. Metal loss through galactic winds is also commonly invoked to explain the low metal content of dwarf galaxies. Our main aim in this paper is to show that galactic mass cannot be the only parameter determining the fraction of metals lost by a galaxy. In particular, the distribution of gas must play an equally important role. We perform 2-D chemo-dynamical simulations of galaxies characterized by different gas distributions, masses and gas fractions. The gas distribution can change the fraction of lost metals through galactic winds by up to one order of magnitude. In particular, disk-like galaxies tend to loose metals more easily than roundish ones. Consequently, also the final metallicities attained by models with the same mass but with different gas distributions can vary by up to one dex. Confirming previous studies, we also show that the fate of gas and freshly produced metals strongly depends on the mass of the galaxy. Smaller galaxies (with shallower potential wells) more easily develop large-scale outflows, therefore the fraction of lost metals tends to be higher.

The physics of the fundamental metallicity relation

We present a simple, redshift-independent analytic model that explains the local Fundamental Metallicity Relation (FMR), taking into account the physical processes of star formation, inflow of metal-poor intergalactic medium (IGM) gas, and the outflow of metal rich interstellar medium (ISM) gas. We show that the physics of the FMR can be summarised as follows: for massive galaxies with stellar mass M_* >= 10^11 solar masses, ISM metal enrichment due to star formation is compensated by inflow of metal poor IGM gas, leading to a constant value of the gas metallicity with star formation rate (SFR); outflows are rendered negligible as a result of the large potential wells of these galaxies. On the other hand, as a result of their smaller SFR, less massive galaxies produce less heavy elements that are also more efficiently ejected due to their shallow potential wells; as a result, for a given M_*, the gas metallicity decreases with SFR. For such galaxies, the outflow efficiency determines both the slope, and the knee of the metallicity-SFR relation. Without changing any parameters, this simple model is also successfully matched to the gas fraction - gas metallicity relation observed for a sample of about 260 nearby galaxies.

Seeking Observable Imprints of Small-Scale Structure on the Properties of Dark Matter Haloes

AbstractThe characteristic prediction of the Cold Dark Matter (CDM) model of cosmological structure formation is that the Universe should contain a wealth of small-scale structure—low-mass dark matter haloes and subhaloes. However, galaxy formation is inefficient in their shallow potential wells and so we expect these low-mass haloes and subhaloes to be dark. Can we tell the difference between a Universe in which these low-mass haloes are present but dark and one in which they never formed, thereby providing a robust test of the CDM model? We address this question using cosmological N-body simulations to examine how properties of low-mass haloes that are potentially accessible to observation, such as their spatial clustering, rate of accretions and mergers onto massive galaxies, and the angular momentum content of massive galaxies, differ between a fiducial ΛCDM model and dark matter models in which low-mass halo formation is suppressed. Adopting an effective cut-off mass scale Mcut below which small-scale power is suppressed in the initial conditions, we study dark matter models in which Mcut varies between 5×109h−1M⊙ and 1011h−1M⊙, equivalent to the host haloes of dwarf and low-mass galaxies. Our results show that both the clustering strength of low-mass haloes around galaxy-mass primaries and the rate at which they merge with these primaries are sensitive to the assumed value of Mcut; in contrast, suppressing low-mass halo formation has little influence on the angular momentum content of galaxy-mass haloes—it is the quiescence or violence of a halo's assembly history that has a more marked effect. However, we expect that measuring the effect on spatial clustering or the merger rate is likely to be observationally difficult for realistic values of Mcut, and so isolating the effect of this small-scale structure would appear to be remarkably difficult to detect, at least in the present day Universe.

THE EXTENSIVE AGE GRADIENT OF THE CARINA DWARF GALAXY

The evolution of small systems such as dwarf spheroidal galaxies (dSph) is likely to have been a balance between external environmental effects and internal processes within their own relatively shallow potential wells. Assessing how strong such environmental interactions may have been is therefore an important element in understanding the baryonic evolution of dSphs and their derived dark matter distribution. Here we present results from a wide-area CTIO/MOSAIC II photometric survey of the Carina dSph, reaching down to about two magnitudes below the oldest main sequence turn-off (MSTO). This data-set enables us to trace the structure of Carina in detail out to very large distances from its center, and as a function of stellar age. We observe the presence of an extended structure made up primarily of ancient MSTO stars, at distances between 25arcmin-60arcmin from Carina's center, confirming results in the literature that Carina extends well beyond its nominal tidal radius. The large number statistics of our survey reveals features such as isophote twists and tails that had gone undetected in other previous shallower surveys. This is the first time that such unambiguous signs of tidal disruption have been found in a Milky Way "classical" dwarf other than Sagittarius. We also demonstrate the presence of a negative age gradient in Carina directly from its MSTOs, and trace it out to very large distances from the galaxy center. The signs of interaction with the Milky Way make it unclear whether the age gradient was already in place before Carina underwent tidal disruption.

Hybrid InGaN/CdZnO quantum well structures for optoelectronic applications in the short wavelength spectral region

AbstractSpontaneous emission characteristics of hybrid InxGa1 − xN/Cd0.05Zn0.95O quantum well (QW) structures were theoretically investigated by using multi‐band effective mass theory. The transition wavelength of the InGaN/CdZnO QW structure is shown to be changed from 415 to 580 nm when the In content x is varied from 0.1 to 0.3. The conventional InGaN/GaN QW structure shows that its peak intensity linearly decreases with increasing peak wavelength. On the other hand, the InGaN/CdZnO QW structure shows that the spontaneous emission coefficient reaches a maximum at around the peak wavelength of 0.484 µm, which corresponds to x = 0.2. This can be explained by the fact that, in a range of the short peak wavelengths, the InGaN/CdZnO QW structure has a very shallow potential well. In a range of the longer peak wavelengths above 0.47 µm, the InGaN/CdZnO QW structure is expected to have a larger spontaneous emission peak than the InGaN/GaN QW structure. This can be explained by the fact that the former has a reduced internal field compared to the latter.

Mechanism of the direct three-body recombination of atomic ions in a central collision

The detailed dynamics of direct three-body recombination of the Cs+ and Br− heavy ions in the presence of the Xe atom as a third body is studied by the quasiclassical trajectory method. A potential energy surface that quantitatively correctly describes the dynamics of the reverse process of ion formation induced by collisions of CsBr with Xe is used. Depending on the impact parameter of the third body, the stabilization of the product molecule proceeds by several different mechanisms. At impact parameters of bR ≤ 7 au, the stabilization of the nascent molecule is largely controlled the repulsion potential between one of the ions or both the ions and the third body. The energy transferred to the third body does not depend directly on the repulsive potential energy between the ion and the third body. The phase of collision of the ions at the instant of closest approach plays a key role in the process of energy transfer. For collinear collision configurations of the three particles, the ion-Xe shallow potential wells are demonstrated to produce a noticeable effect.

Theoretical calculations on the NaS and NaS+ radicals: electronic structure, spectroscopy and spin-orbit couplings

We used an ab initio methodology for the computation of the potential energy curves of the lowest electronic states of NaS and NaS+ diatomics. Using these highly correlated wavefunctions, we calculated their spin-orbit couplings. The X2Π and the A2Σ+ electronic states of NaS are found to possess deep potential wells. The upper bound electronic states have either shallow potential wells located in the molecular region or potentials of ∼ 1 eV depth located for large NaS distances. For NaS+, our calculations reveal the existence of shallow potentials for all states correlating to the four lowest dissociation limits. Using our potentials, we calculated an accurate set of spectroscopic constants for NaS and NaS+. Most of the data relative to the electronic excited states represent predictions. The spin-orbit induced predissociation of NaS(A2Σ+ is discussed. Finally, our cationic potentials and the NaS(X2Π) potential were used for the prediction of the single ionization spectrum of NaS.

Effective proton-proton interaction and metallization of hydrogen

The effective proton-proton interaction in metallic hydrogen has been calculated for various densities. In the potential of this interaction, which can be represented in the form of a series of perturbation theory in the electron-proton interaction, the second- and third-order terms are taken into account. The second-order term gives a comparatively shallow potential well with one minimum. The position of the minimum corresponds to the equilibrium mutual position of protons in metallic hydrogen. When the third-order term is additionally taken into account, the potential has two characteristic minima; the position of one of them corresponds to the distance between the protons in a hydrogen molecule. The depths of these potential wells depend on the density of the system. At fairly high densities, only the potential well corresponding to the equilibrium position of protons in the metallic phase holds in the proton-proton potential. Owing to the presence of two minima in the effective proton-proton potential, the density of hydrogen at the point of transition to the metallic state can be estimated. Analysis of the effective proton-proton interaction makes it also possible to estimate the possibility of the existence of metallic hydrogen in a stable state at quite low temperatures.

Relative performance of a vibratory energy harvester in mono- and bi-stable potentials

Motivated by the need for broadband vibratory energy harvesting, many research studies have recently proposed energy harvesters with nonlinear characteristics. Based on the shape of their potential function, such devices are classified as either mono- or bi-stable energy harvesters. This paper aims to investigate the relative performance of these two classes under similar excitations and electric loading conditions. To achieve this goal, an energy harvester consisting of a clamped–clamped piezoelectric beam bi-morph is considered. The shape of the harvester's potential function is altered by applying a static compressive axial load at one end of the beam. This permits operation in the mono-stable (pre-buckling) and bi-stable (post-buckling) configurations. For the purpose of performance comparison, the axial load is used to tune the harvester's oscillation frequencies around the static equilibria such that they have equal values in the mono- and bi-stable configurations. The harvester is subjected to harmonic base excitations of different magnitudes and a slowly varying frequency spanning a wide band around the tuned oscillation frequency. The output voltage measured across a purely resistive load is compared over the frequency range considered. Two cases are discussed; the first compares the performance when the bi-stable harvester has deep potential wells, while the second treats a bi-stable harvester with shallow wells. Both numerical and experimental results demonstrate the essential role that the potential shape plays in conjunction with the base acceleration to determine whether the bi-stable harvester can outperform the mono-stable one and for what range of frequencies. Results also illustrate that, for a bi-stable harvester with shallow potential wells, super-harmonic resonances can activate the inter-well dynamics even for a small base acceleration, thereby producing large voltages in the low frequency range.

The diatomic dication CuZn2+ in the gas phase

In the present combined experimental and theoretical study we report the observation of the novel gas-phase dication CuZn(2+) and provide some theoretical insight into the electronic binding of this exotic metastable molecule and its formation mechanism. Using mass spectrometry we have detected four isotopomer signals of CuZn(2+) at half-integer m/z values for ion flight times of about 14 μs. CuZn(2+) was unambiguously identified by its isotopic abundance. High-current energetic Ar(+) ion bombardment of a brass surface was used for its production. Subsequent dication formation was found to take place in the ion extraction region of our mass spectrometer several tens of microns in front of the sputtered brass surface. The dication formation mechanism appears to be resonant electron transfer in soft gas-phase collisions between sputter-ejected singly charged CuZn(+) molecular ions and incoming Ar(+) projectiles. This conclusion is supported by our theoretical study that obtained an ionization energy of CuZn(+) of 15.75 eV, in excellent agreement with both the experimental and calculated ionization energy of Ar (15.76 and 15.67 eV, respectively). The ground state of CuZn(2+) is found to be a metastable one with a very shallow potential well at an internuclear equilibrium distance of about 2.7 Å the dissociation energy being very difficult to estimate. Interestingly, spin-orbit corrections are found to be necessary to get an adequate description of the metastable state of CuZn(2+), whereas relativistic corrections have no effects on neutral CuZn nor on CuZn(+).

CLARA’s view on the escape fraction of Lyman α photons in high-redshift galaxies

Using CLARA (Code for Lyman Alpha Radiation Analysis) we constrain the escape fraction of Lyman-Alpha radiation in galaxies in the redshift range 5<z<7, based on the MareNostrum High-z Universe, a SPH cosmological simulation with more than 2 billion particles. We approximate Lyman-Alpha Emitters (LAEs) as dusty gaseous slabs with Lyman-Alpha radiation sources homogeneously mixed in the gas. Escape fractions for such a configuration and for different gas and dust contents are calculated using our newly developed radiative transfer code CLARA. The results are applied to the MareNostrum High-z Universe numerical galaxies. The model shows a weak redshift evolution and good agreement with estimations of the escape fraction as a function of reddening from observations at z \sim 2.2 and z \sim 3. We extend the slab model by including additional dust in a clumpy component in order to reproduce the UV con- tinuum luminosity function and UV colours at redshifts z>~5. The LAE Luminosity Function (LF) based on the extended clumpy model reproduces broadly the bright end of the LF derived from observations at z \sim 5 and z \sim 6. At z \sim 7 our model over-predicts the LF by roughly a factor of four, presumably because the effects of the neutral intergalactic medium are not taken into account. The remaining tension between the observed and simulated faint end of the LF, both in the UV-continuum and Lyman-Alpha at redshifts z \sim 5 and z \sim 6 points towards an overabundance of simulated LAEs hosted in haloes of masses 1.0x10^10h-1Msol < Mh < 4.0x10^10h-1Msol. Given the difficulties in explaining the observed overabundance by dust absorption, a probable origin of the mismatch are the high star formation rates in the simulated haloes around the quoted mass range. A more efficient supernova feedback should be able to regulate the star formation process in the shallow potential wells of these haloes.

Impact of supernova feedback on the Tully-Fisher relation

Recent observational results found a bend in the Tully-Fisher Relation in such a way that low mass systems lay below the linear relation described by more massive galaxies. We intend to investigate the origin of the observed features in the stellar and baryonic Tully-Fisher relations and analyse the role played by galactic outflows on their determination. Cosmological hydrodynamical simulations which include Supernova feedback were performed in order to follow the dynamical evolution of galaxies. We found that Supernova feedback is a fundamental process in order to reproduce the observed trends in the stellar Tully-Fisher relation. Simulated slow rotating systems tend to have lower stellar masses than those predicted by the linear fit to the massive end of the relation, consistently with observations. This feature is not present if Supernova feedback is turned off. In the case of the baryonic Tully-Fisher relation, we also detect a weaker tendency for smaller systems to lie below the linear relation described by larger ones. This behaviour arises as a result of the more efficient action of Supernovae in the regulation of the star formation process and in the triggering of powerful galactic outflows in shallower potential wells which may heat up and/or expel part of the gas reservoir.