215 research outputs found
Valence Virtual Orbitals: An unambiguous ab initio quantification of the LUMO concept
Many chemical concepts hinge on the notion of an orbital called the lowest unoccupied molecular orbital, or LUMO. This hypothetical orbital and the much more concrete highest occupied molecular orbital (HOMO) constitute the two “frontier orbitals”, which rationalize a great deal of chemistry. A viable LUMO candidate should have a sensible energy value, a realistic shape with amplitude on those atoms where electron attachment or reduction or excitation processes occur, and often an antibonding correspondence to one of the highest occupied MOs. Unfortunately, today’s quantum chemistry calculations do not yield useful empty orbitals. Instead, the empty canonical orbitals form a large sea of orbitals, where the interesting valence antibonds are scrambled with the basis set’s polarization and diffuse augmentations. The LUMO is thus lost within a continuum associated with a detached electron, as well as many Rydberg excited states. A suitable alternative to the canonical orbitals is proposed, namely, the valence virtual orbitals. VVOs are found by a simple algorithm based on singular value decomposition, which allows for the extraction of all valence-like orbitals from the large empty canonical orbital space. VVOs are found to be nearly independent of the working basis set. The utility of VVOs is demonstrated for construction of qualitative MO diagrams, for prediction of valence excited states, and as starting orbitals for more sophisticated calculations. This suggests that VVOs are a suitable realization of the LUMO, LUMO + 1, ... concept. VVO generation requires no expert knowledge, as the number of VVOs sought is found by counting s-block atoms as having only a valence s orbital, transition metals as having valence s and d, and main group atoms as being valence s and p elements. Closed shell, open shell, or multireference wave functions and elements up to xenon may be used in the present program
Near-surface dynamics of a gas bubble collapsing above a crevice
The impact of a collapsing gas bubble above rigid, notched walls is
considered. Such surface crevices and imperfections often function as bubble
nucleation sites, and thus have a direct relation to cavitation-induced erosion
and damage structures. A generic configuration is investigated numerically
using a second-order-accurate compressible multi-component flow solver in a
two-dimensional axisymmetric coordinate system. Results show that the crevice
geometry has a significant effect on the collapse dynamics, jet formation,
subsequent wave dynamics, and interactions. The wall-pressure distribution
associated with erosion potential is a direct consequence of development and
intensity of these flow phenomena.Comment: 21 pages, 16 figures, submitted to the Journal of Fluid Mechanic
Near-surface dynamics of a gas bubble collapsing above a crevice
The impact of a collapsing gas bubble above rigid, notched walls is considered. Such surface crevices and imperfections often function as bubble nucleation sites, and thus have a direct relation to cavitation-induced erosion and damage structures. A generic configuration is investigated numerically using a second-order accurate compressible multi-component flow solver in a two-dimensional axisymmetric coordinate system. Results show that the crevice geometry has a significant effect on the collapse dynamics, jet formation, subsequent wave dynamics and interactions. The wall-pressure distribution associated with erosion potential is a direct consequence of development and intensity of these flow phenomena
KD Diagnosis Does Not Increase Cardiovascular Risk in Children According to Dynamic Intima–Media Roughness Measurements
Background: Kawasaki Disease (KD) is a generalized vasculitis in childhood with possible long-term impact on cardiovascular health besides the presence of coronary artery lesions. Standard vascular parameters such as carotid intima–media thickness (cIMT) have not been established as reliable markers of vascular anomalies after KD. The carotid intima–media roughness (cIMR) representing carotid intimal surface structure is considered a promising surrogate marker for predicting cardiovascular risk even beyond cIMT. We therefore measured cIMR in patients with a history of KD in comparison to healthy controls to investigate whether KD itself and/or KD key clinical aspects are associated with cIMR alterations in the long-term. Methods: We assessed cIMR in this case-control study (44 KD, mean age in years (SD); 13.4 (7.5); 36 controls, mean age 12.1 (5.3)) approximately matched by sex and age. Different clinical outcomes such as the coronary artery status and acute phase inflammation data were analyzed in association with cIMR values. Results: When comparing all patients with KD to healthy controls, we detected no significant difference in cIMR. None of the clinical parameters indicating the disease severity, such as the persistence of coronary artery aneurysm, were significantly associated with our cIMR values. However, according to our marginally significant findings (p = 0.044), we postulate that the end-diastolic cIMR may be rougher than the end-systolic values in KD patients. Conclusions: We detected no significant differences in cIMR between KD patients and controls that could confirm any evidence that KD predisposes patients to a subsequent general arteriopathy. Our results, however, need to be interpreted in the light of the low number of study participants
CHANG-ES IV: Radio continuum emission of 35 edge-on galaxies observed with the Karl G. Jansky Very Large Array in D-configuration, Data Release 1
We present the first part of the observations made for the Continuum Halos in
Nearby Galaxies, an EVLA Survey (CHANG-ES) project. The aim of the CHANG-ES
project is to study and characterize the nature of radio halos, their
prevalence as well as their magnetic fields, and the cosmic rays illuminating
these fields. This paper reports observations with the compact D configuration
of the Karl G. Jansky Very Large Array (VLA) for the sample of 35 nearby
edge-on galaxies of CHANG-ES. With the new wide bandwidth capabilities of the
VLA, an unprecedented sensitivity was achieved for all polarization products.
The beam resolution is an average of 9.6" and 36" with noise levels reaching
approximately 6 and 30 microJy per beam for C- and L-bands, respectively
(robust weighting). We present intensity maps in these two frequency bands (C
and L), with different weightings, as well as spectral index maps, polarization
maps, and new measurements of star formation rates (SFRs). The data products
described herein are available to the public in the CHANG-ES data release
available at www.queensu.ca/changes. We also present evidence of a trend among
galaxies with larger halos having higher SFR surface density, and we show, for
the first time, a radio continuum image of the median galaxy, taking advantage
of the collective signal-to-noise ratio of 30 of our galaxies. This image shows
clearly that a typical spiral galaxy is surrounded by a halo of magnetic fields
and cosmic rays.Comment: 70 pages, of which 35 pages present the data of each galax
CHANG-ES XI: Circular Polarization in the Cores of Nearby Galaxies
We detect 5 galaxies in the CHANG-ES (Continuum Halos in Nearby Galaxies --
an EVLA Survey) sample that show circular polarization (CP) at L-band in our
high resolution data sets. Two of the galaxies (NGC~4388 and NGC~4845) show
strong Stokes \%, two (NGC~660 and NGC~3628) have
values of \%, and NGC~3079 is a marginal detection at \%. The two strongest galaxies also have the most luminous X-ray
cores and the strongest internal absorption in X-rays. We have expanded on our
previous Faraday conversion interpretation and analysis and provide analytical
expressions for the expected signal for a general case in which the cosmic
ray electron energy spectral index can take on any value. We provide examples
as to how such expressions could be used to estimate magnetic field strengths
and the lower energy cutoff for CR electrons. Four out of our detections are
{\it resolved}, showing unique structures, including a {\it jet} in NGC~4388
and a CP `conversion disk' in NGC~4845. The conversion disk is inclined to the
galactic disk but is perpendicular to a possible outflow direction. Such CP
structures have never before been seen in any galaxy to our knowledge. None of
the galaxy cores show linear polarization at L-band. Thus CP may provide a
unique probe of physical conditions deep into radio AGNs.Comment: 30 pages, 4 figures, accepted to MNRA
Continuum Halos in Nearby Galaxies -- an EVLA Survey (CHANG-ES) -- II: First Results on NGC 4631
We present the first results from the CHANG-ES survey, a new survey of 35
edge-on galaxies to search for both in-disk as well as extra-planar radio
continuum emission. The motivation and science case for the survey are
presented in a companion paper (Paper I). In this paper (Paper II), we outline
the observations and data reduction steps required for wide-band calibration
and mapping of EVLA data, including polarization, based on C-array test
observations of NGC 4631.
With modest on-source observing times (30 minutes at 1.5 GHz and 75 minutes
at 6 GHz for the test data) we have achieved best rms noise levels of 22 and
3.5 Jy beam at 1.5 GHz and 6 GHz, respectively. New disk-halo
features have been detected, among them two at 1.5 GHz that appear as loops in
projection. We present the first 1.5 GHz spectral index map of NGC 4631 to be
formed from a single wide-band observation in a single array configuration.
This map represents tangent slopes to the intensities within the band centered
at 1.5 GHz, rather than fits across widely separated frequencies as has been
done in the past and is also the highest spatial resolution spectral index map
yet presented for this galaxy. The average spectral index in the disk is
indicating that the emission is
largely non-thermal, but a small global thermal contribution is sufficient to
explain a positive curvature term in the spectral index over the band. Two
specific star forming regions have spectral indices that are consistent with
thermal emission. Polarization results (uncorrected for internal Faraday
rotation) are consistent with previous observations and also reveal some new
features. On broad scales, we find strong support for the notion that magnetic
fields constrain the X-ray emitting hot gas.Comment: Accepted to the Astronomical Journal, Version 2 changes: Added
acknowledgement to NRA
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