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 $V/I\,\equiv\,m_C\,\sim\,2$\%, two (NGC~660 and NGC~3628) have values of $m_C\sim \,0.3$\%, and NGC~3079 is a marginal detection at $m_C\sim \,0.2$\%. The two strongest $m_C$ 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 $V$ 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 $\mu$Jy beam$^{-1}$ 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 $\bar\alpha_{1.5 GHz}\,=\,-0.84\,\pm\,0.05$ 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