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At least 127 records · Page 7

A potential-energy surface study of the 2A1 and low-lying dissociative states of the methoxy radical

Accurate, ab initio quantum chemical techniques are applied in the present study of low lying bound and dissociative states of the methoxy radical at C3nu conformations, using a double zeta quality basis set that is augmented with polarization and diffuse functions. Excitation energy estimates are obtained for vertical excitation, vertical deexcitation, and system origin. The rate of methoxy photolysis is estimated to be too small to warrant its inclusion in atmospheric models.

Jackels, C. F.↗

Theoretical study of NH2 - Potential curves, transition moments, and photodissociation cross sections

Photodissociation cross sections from the ground state of NH2 have been calculated using a pseudodiatomic model. The potential curves needed in these calculations, functions of one NH bond length, were obtained by ab initio MCSCF calculations on the five lowest doublet states of NH2 using a contracted Gaussian basis set of double zeta quality augmented by polarization and Rydberg functions. Transition dipole moments between the ground and excited states were evaluated using MCSCF wave functions.

Saxon, R. P.↗

Light propagation and the distance-redshift relation in a realistic inhomogeneous universe

The propagation of light rays in a clumpy universe constructed by cosmological version of the post-Newtonian approximation was investigated. It is shown that linear approximation to the propagation equations is valid in the region where zeta is approximately less than 1 even if the density contrast is much larger than unity. Based on a gerneral order-of-magnitude statistical consideration, it is argued that the linear approximation is still valid where zeta is approximately greater than 1. A general formula for the distance-redshift relation in a clumpy universe is given. An explicit expression is derived for a simplified situation in which the effect of the gravitational potential of inhomogeneities dominates. In the light of the derived relation, the validity of the Dyer-Roeder distance is discussed. Also, statistical properties of light rays are investigated for a simple model of an inhomogeneous universe. The result of this example supports the validity of the linear approximation.

Futamase, Toshifumi↗

Computed Minimum Energy Pathway for Isomerization in Ketene

A minimum energy pathway for interchange of the CH groups in ketene via a C2v structure has been obtained using complete active space self consistent field (CASSCF) derivative methods with a polarized valence double zeta basis set to define the reaction pathway followed by multi-reference internally contracted configuration interaction (ICCI) calculations with a [3s3p2d/3s2p] basis set to determine the energetics. Qualitatively, the C2v structure is found to be a shallow minimum on the potential energy surface separated from ketene by a small barrier (0.2 kcal/mol), a second minimum, and a larger barrier (3.0 kcal/mol). The minimum energy pathway leading from the C2v minimum to ketene starts by simultaneous rotation of the farther CH group out of the plane and away from the oxygen followed by increase of the CCO angle and subsequent 1,2-migration of the H of the nearer CH group toward the carbon of the farther CH group.

Walch, Stephen P.↗

Theoretical study of the dipole moment of oxygen monofluoride (OF)

The ground-state potential curve and dipole-moment function of OF are calculated theoretically using the complete active-space self-consistent-field levels, externally contracted configuration-interaction levels, or multireference (singles plus doubles) configuration-interaction levels. Both an extended Gaussian basis set and a double-zeta-plus-polarization basis set were applied. The results are presented in extensive tables and graphs. Best results are achieved using a large Gaussian basis set and taking the valence-correlation energy into account. It is suggested that OF may best be detected by its laser-magnetic-resonance spectrum in the IR.

Langhoff, S. R.↗

The Remarkable I 2 O 3 Molecule: A New View from Theory

Atmospheric iodine chemistry has garnered increasing attention as a result of increased iodine emissions. A key subset of this chemistry involves iodine oxides (I 2 O 2–5 ), which serve as precursors to particle formation. Among these, I 2 O 3 is the simplest iodine oxide involved in particle formation, but it has remained undetected in the atmosphere. Previous theoretical studies have characterized this peculiar molecule, primarily using energies to refine geometries obtained at low levels of theory. Due to the reemerging interest in I 2 O 3 , this study presents geometries optimized at the CCSD(T)/aug-cc-pwCVTZ-PP level of theory─marking the first instance, to the best of our knowledge, where this system has been studied exclusively with CCSD(T). Harmonic vibrational frequencies were computed at the same level of theory. Final energetics were obtained using the very high level CCSDT(Q) method with basis sets up to quintuple-zeta cardinality (aug-cc-pwCV5Z-PP) and extrapolated to the CBS limit to yield CCSDT(Q)/CBS//CCSD(T)/aug-cc-pwCVTZ-PP energies. These energies include harmonic zero-point vibrational energy corrections and scalar relativistic energy corrections. Additionally, this study discovers new isomers along the I 2 O 3 potential energy surface, a novel contribution to the field. The performance of different computational methods and DFT functionals commonly used in atmospheric chemistry is also assessed relative to high-level theoretical methods.

basis sets↗

Ground and lower excited states of methyl peroxy, CH3O2, radical - A computational investigation

The ground and lower excited states of methyl peroxy, CH3O2, radical have been investigated at the selected pseudofirst-order configuration interaction level by use of a double-zeta basis set. Selected singles and doubles calculations using a polarized double-zeta basis have been carried out on the two lowest states in the A-double prime symmetry. Dissociation energies with respect to CH3O2 yields CH3 + O2 and CH3O + O are computed to be 2.01 and 3.37 eV, respectively. Curve crossings between various states and photodissociation products are discussed and the dipole moment along various slices through the potential energy surface is evaluated.

Jafri, Jawed A.↗

Longitudinal Laminar Flow Between Cylinders Arranged in Regular Array

The increasing complexity of heat transfer and process situations which involve fluid flow has demanded the frequent use of flow passages of unusual geometrical configuration. The present investigation is concerned with one such novel configuration, namely the longitudinal flow between solid cylindrical rods which are arranged in regular array. A schematic diagram of the situation under study. The rods may be located either in triangular or square array. The flow will be taken to be laminar and fully developed. The aim of this analysis is to determine the pressure drop, shear stress, and velocity-distribution characteristics of the system. The starting point of this study is the basic law of momentum conservation. The resulting differential equation has been solved in an approximate, but almost exact, manner by the use of truncated trigonometric series. Results are obtained over a wide range of porosity values for both the triangular and square arrays. Heat transfer has not been considered. The configuration under investigation has potential application in compact heat exchangers for nuclear reactors and other situations. Further the results should also be of interest in the theory of flow through unconsolidated porous beds (ia, 9a). The only related analytical work known to the authors is that of Emersleben (S), who considered only the square array. His rather involved solution, based on complex zeta functions, appears to be valid only at high porosities. Experiments covering a porosity range of 0.093 to 0.984 have been made by Sullivan (4) using parallel-oriented fibers, most of the tests being for fibers in random array. These previous investigations will be compared with the present theory in a later section.

Sparrow, E. M.↗

Exploring the Tl 2H 2 potential energy surface: A comparative analysis with group 13 systems and experiment

Abstract Thallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet TlH potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug‐cc‐pwCVQZ‐PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug‐cc‐pwCVTZ‐PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple‐zeta cardinality (aug‐cc‐pwCV5Z‐PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero‐point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 MH (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

Chemistry↗

Expansion of solar-terrestrial low-beta plasmoid

A magnetized plasma system confined inside a finite volume may expand (or contract) when its surrounding pressure changes. In this paper, two possible expanding processes of a low-beta plasmoid are discussed: (1) linear expansion and (2) expansion with fixed footpoints of field lines. The constant-zeta expansion, discussed in this paper, may maintain a low-beta plasmoid in a nearly force-free state during the expanding process. This simple model is applied to the magnetic clouds observed in the interplanetary space. The estimated scale size and expanding speed of the magnetic cloud are found to be in reasonable agreement with the observation. The energy conversion process is investigated: the free 'magnetic potential energy' stored in a magnetized system, which is pressed by external pressure, may be released to accelerate the plasma. The concept of a 'magnetic burst' is briefly discussed.

Yang, Wei-Hong↗

Computational solution of chemistry problems

AB initio quantum chemical techniques have been used to investigate weakly bound complexes of H2O and SO2. An energy gradient program was used to locate stable structures for the H2O, SO2 complexes, and SCF calculations were carried out to determine the binding energies of complexes with multiple water molecules. A 4-31G basis set was used for most potential energy searches. More accurate basis sets including a generally contracted basis set with d orbitals on the sulfur were used for geometry and binding energy verification. For single water complexes, five different stable geometries were located with binding energies between 4 and 11 Kcal mol(-1), suggesting a binding shell for H2O around SO2 and a mechanism for the formation of an SO2-containing water droplet. Calculations on one of the complexes utilizing a larger double zeta basis and d functions on the sulfur atom lead to adjusted binding energies in the range 3 to 8 Kcal mol(-1). Very little charge transfer between SO2 and H2O was present. Addition of more than one H2O was found to be energetically favorable although the addition of the fourth water in certain geometries did not increase the stability of the complex. An alternative mechanism for the tropospheric gas phase production of acid rain is suggested.

Ake, Robert L.↗

Recent Increasing Trend in October–November Caribbean Tropical Cyclone Activity

October–November Caribbean tropical cyclone (TC) activity has significant impacts for both the Caribbean islands and Central America (e.g., Hurricanes Eta and Iota in 2020). October–November Caribbean TCs can also track northward and make continental United States landfall, resulting in substantial damage and fatalities (e.g., Hurricane Michael in 2018 and Delta and Zeta in 2020). We find significant increasing trends in October–November Caribbean hurricanes, rapidly intensifying hurricanes (winds increasing by ≥15 m s −1 within 24 hr), and landfalling hurricanes during the global satellite era (1979–present). Since 1979, we also observe significant warming trends in the western Atlantic Warm Pool and anomalous relative cooling in the eastern Pacific during October–November. These trends yield a more conducive dynamic and thermodynamic environment for Caribbean TCs, including reductions in Caribbean vertical wind shear, increases in Caribbean potential intensity, and a more TC-conducive African easterly jet.

Klotzbach, P. J. [Colorado State Univ., Fort Colli↗

The Fraternal Twins of Quartet O4(+)

Eleven stationary geometries of quartet O4(+) have been studied by ab initio methods. The geometries were optimized at the Complete Active Space Self-Consistent Field (CASSCF) level of theory and the energies were calculated by the multiconfigurational second order pertubation method (CASPT2), using Double-Zeta Plus polarization (DZP), Triple-Zeta Plus Double Polarization (TZ2P), average Atomic Natural Orbital (ANO) (5s4p2d) and average ANO (6s5p3d2f) basis sets. The rectangular and trans-planar structures are found to be the most stable, with an energy barrier to conversion between the two at the threshold of dissociation. Both have a delocalized hole and are stable relative to separated 02 and 02(+)by 11.0 and 11.5 kcal/mol for the rectangular and the 2 trans-planar structure, respectively, compared with the experimentally deduced energy in the range of 9.2 to 10.8 kcal/mol. The adiabatic ionization potentials of 04 and 02 are computed to be 11.67 and 12.21 eV, while experimental values are 11.66 and 12.07 eV, respectively. The vibrational frequencies have been computed for all degrees of freedom at the CASSCF level of theory. Symmetry breaking is found to be a particular problem in the computation of the antisymmetric stretch frequency for the delocalized structures at the CASSCF level of theory. Attempts to rectify these problems using the restricted active space self-consistent field (RASSCF) method leads to additional difficulties, but further analysis yields insight into the symmetry breaking and problems with earlier calculations. Finally, a nonorthogonal configuration interaction (CI) calculation based on the interaction of localized CASSCF wave functions using the Complete Active Space State Interation (CASSI) method leads to a balanced treatment of the antisymmetric stretch which is free from symmetry breaking. The study explains the four most prominent absorption frequencies observed in the partially unassigned IR spectrum of O4(+) isolated in solid neon as the antisymmetric OO stretch, and the combination band of the symmetric and antisymmetric 00 stretch of both the rectangular and trans-planar structures.

Lindh, Roland↗

A search for interstellar scandium

The resonance line of Sc II at 3642.785 A has been sought in the interstellar spectrum of Zeta Oph, resulting in an upper limit N(Sc II) not greater than 8.6 billion/sq cm and a depletion of this element at least by a factor of 200, if Sc III contributes a negligible column density. The present upper limit may be somewhat below the level expected under the grain-formation model for interstellar depletions, and is consistent with the abundance expected if the depletions are due to gas-grain collisions. The new limit on this element helps to support the hypothesis that species within a specific range of ionization potential are preferentially depleted.

Snow, T. P., Jr.↗

Can Eccentric Debris Disks Be Long-lived? A First Numerical Investigation and Application to Zeta(exp 2) Reticuli

Context. Imaging of debris disks has found evidence for both eccentric and offset disks. One hypothesis is that they provide evidence for massive perturbers, for example, planets or binary companions, which sculpt the observed structures. One such disk was recently observed in the far-IR by the Herschel Space Observatory around Zeta2 Reticuli. In contrast with previously reported systems, the disk is significantly eccentric, and the system is several Gyr old. Aims. We aim to investigate the long-term evolution of eccentric structures in debris disks caused by a perturber on an eccentric orbit around the star. We hypothesise that the observed eccentric disk around Zeta2 Reticuli might be evidence of such a scenario. If so, we are able to constrain the mass and orbit of a potential perturber, either a giant planet or a binary companion. Methods. Analytical techniques were used to predict the effects of a perturber on a debris disk. Numerical N-body simulations were used to verify these results and further investigate the observable structures that may be produced by eccentric perturbers. The long-term evolution of the disk geometry was examined, with particular application to the Zeta2 Reticuli system. In addition, synthetic images of the disk were produced for direct comparison with Herschel observations. Results. We show that an eccentric companion can produce both the observed offsets and eccentric disks. These effects are not immediate, and we characterise the timescale required for the disk to develop to an eccentric state (and any spirals to vanish). For Zeta2 Reticuli, we derive limits on the mass and orbit of the companion required to produce the observations. Synthetic images show that the pattern observed around Zeta2 Reticuli can be produced by an eccentric disk seen close to edge-on, and allow us to bring additional constraints on the disk parameters of our model (disk flux and extent). Conclusions. We conclude that eccentric planets or stellar companions can induce long-lived eccentric structures in debris disks. Observations of such eccentric structures thus provide potential evidence of the presence of such a companion in a planetary system. We considered the specific example of Zeta2 Reticuli, whose observed eccentric disk can be explained by a distant companion (at tens of AU) on an eccentric orbit (ep greater than approx. 0.3).

planetary systems↗

High-Resolution Near-Infrared Spectroscopy of an Equivalent Width-Selected Sample of Starbursting Dwarf Galaxies

Spectroscopic observations from the Large Binocular Telescope and the Very Large Telescope reveal kinematically narrow lines (approx. 50 km/s) for a sample of 14 Extreme Emission Line Galaxies (EELGs) at redshifts 1.4 < zeta < 2.3. These measurements imply that the total dynamical masses of these systems are low ( 3 × 10(exp 9) M). Their large [O III]5007 equivalent widths (500 − 1100 A) and faint blue continuum emission imply young ages of 10−100 Myr and stellar masses of 10(exp 8)−10(exp 9) M, confirming the presence of a violent starburst. The stellar mass formed in this vigorous starburst phase thus represents a large fraction of the total (dynamical) mass, without a significantly massive underlying population of older stars. The occurrence of such intense events in shallow potentials strongly suggests that supernova-driven winds must be of critical importance in the subsequent evolution of these systems.

Spectroscopy↗

On the low-lying states of MgO. II

Using a double zeta plus polarization basis set of Slater orbitals, full valence MCSCF (FVMCSCF) calculations were performed for the low-lying states of MgO. For each state the FVMCSCF calculations were used to identify the important configurations which are then used in the MCSCF calculation and subsequently as references in a single and double excitation CI calculation. This approach is found to treat all states equivalently, with the maximum error in the computed transition energies and equilibrium bond lengths of 800/cm and approximately 0.03 A, respectively. The b 3 Sigma + state which has yet to be characterized experimentally is predicted to have a transition energy of approximately 8300/cm and a bond length of 1.79 A. A spectroscopic analysis of the potential curves indicates that their shapes are in quite reasonable agreement with the range of experimental results.

Bauschlicher, C. W., Jr.↗

Electric Field Induced Interfacial Instabilities

The study of the interface in a charge-free, critical and near-critical binary fluid in the presence of an externally applied electric field is presented. At sufficiently large fields, the interface between the two phases of the binary fluid should become unstable and exhibit an undulation with a predefined wavelength on the order of the capillary length. As the critical point is approached, this wavelength is reduced, potentially approaching length-scales such as the correlation length or critical nucleation radius. At this point the critical properties of the system may be affected. In this paper, the flat interface of a marginally polar binary fluid mixture is stressed by a perpendicular alternating electric field and the resulting instability is characterized by the critical electric field E(sub c) and the pattern observed. The character of the surface dynamics at the onset of instability is found to be strongly dependent on the frequency f of the field applied. The plot of E(sub c) vs. f for a fixed temperature shows a sigmoidal shape, whose low and high frequency limits are well described by a power-law relationship, E(sub c) = epsilon(exp zeta) with zeta = 0.35 and zeta = 0.08, respectively. The low-limit exponent compares well with the value zeta = 4 for a system of conducting and non-conducting fluids. On the other hand, the high-limit exponent coincides with what was first predicted by Onuki. The instability manifests itself as the conducting phase penetrates the non-conducting phase. As the frequency increases, the shape of the pattern changes from an array of bifurcating strings to an array of column-like (or rod-like) protrusions, each of which spans the space between the plane interface and one of the electrodes. For an extremely high frequency, the disturbance quickly grows into a parabolic cone pointing toward the upper plate. As a result, the interface itself changes its shape from that of a plane to that of a high sloping pyramid.

Kusner, Robert E.↗