The spin-forbidden vacuum-ultraviolet absorption spectrum of 14N15N.

Photoabsorption spectra of 14N15N were recorded at high resolution with a vacuum-ultraviolet Fourier-transform spectrometer fed by synchrotron radiation in the range of 81-100 nm. The combination of high column density (3 × 1017 cm-2) and low temperature (98 K) allowed for the recording of weak spin-forbidden absorption bands' exciting levels of triplet character. The triplet states borrow intensity from 1Πu states of Rydberg and valence character while causing their predissociation. New predissociation linewidths and molecular constants are obtained for the states C3Πu(v = 7, 8, 14, 15, 16, 21), G3Πu(v = 0, 1, 4), and F3Πu(v = 0). The positions and widths of these levels are shown to be well-predicted by a coupled-Schrödinger equation model with empirical parameters based on experimental data on 14N2 and 15N2 triplet levels.

Wigner Near-Threshold Effects in the Photoelectron Angular Distribution of NO2.

High-resolution velocity map imaged photoelectron spectra of the nitrite anion NO2- are measured over a range of photodetachment wavelengths between 355 and 550 nm, resolving the vibrational and rotational structure of the NO2(X̃2A1) + e- ← NO2-(X̃1A1) + hν transition. A full rotational band model is constructed to define the spectroscopic constants of both the neutral and the lesser studied anion ground states. The corresponding photoelectron angular distributions are characterized by a large positive anisotropy parameter, with ß ≈ 1.5 gradually increasing to ß ≈ 1.7 upon approaching the threshold. However, at very low kinetic energies, within 0.1 eV of the threshold, ß dramatically drops to 0. This behavior is a consequence of the Wigner near-threshold selectivity of the electron partial-wave cross sections, whereby an atomic p-like orbital character adjacent to the threshold is favored. The full kinetic energy dependence of ß is reproduced by a new mixed spd orbital model, yielding a NO2-(X̃1A1) molecular-orbital decomposition of 2% p, 44% s, and 54% d character.

The dicarbon bonding puzzle viewed with photoelectron imaging.

Bonding in the ground state of C[Formula: see text] is still a matter of controversy, as reasonable arguments may be made for a dicarbon bond order of [Formula: see text], [Formula: see text], or [Formula: see text]. Here we report on photoelectron spectra of the C[Formula: see text] anion, measured at a range of wavelengths using a high-resolution photoelectron imaging spectrometer, which reveal both the ground [Formula: see text] and first-excited [Formula: see text] electronic states. These measurements yield electron angular anisotropies that identify the character of two orbitals: the diffuse detachment orbital of the anion and the highest occupied molecular orbital of the neutral. This work indicates that electron detachment occurs from predominantly [Formula: see text]-like ([Formula: see text]) and [Formula: see text]-like ([Formula: see text]) orbitals, respectively, which is inconsistent with the predictions required for the high bond-order models of strongly [Formula: see text]-mixed orbitals. This result suggests that the dominant contribution to the dicarbon bonding involves a double-bonded configuration, with 2[Formula: see text] bonds and no accompanying [Formula: see text] bond.

Fourier-transform-spectroscopic photoabsorption cross sections and oscillator strengths for the S2 BΣu-3-XΣg-3 system.

Photoabsorption cross sections and oscillator strengths for the strong, predissociating vibrational bands, v ≥ 11, in the S2 BΣu-3-XΣg-3(v,0) system are reported. Absorption measurements were undertaken on S2 vapor produced by a radio-frequency discharge through H2S seeded in helium, and also in a two-temperature sulfur furnace, at temperatures of 370 K and 823 K, respectively. S2 column densities were determined in each source by combining experimental line strengths in low-v non-predissociating B - X bands (v < 7) with calculated line f-values based on measured radiative lifetimes and calculated branching ratios. The broad-band capabilities of two vacuum-ultraviolet Fourier-transform spectrometers, used with instrumental resolutions of 0.22 cm-1 and 0.12 cm-1, respectively, allowed for simultaneous recordings of both non-predissociating and predissociating bands, thus placing the predissociating-band cross sections on a common absolute scale. Uncertainties in the final cross section datasets are estimated to be 15% for the 370-K vapor and 10% for the 823-K vapor. The experimental cross sections are used to inform a detailed predissociation model of the B(v) levels in Paper II [Lewis et al., J. Chem. Phys. 148, 244303 (2018)]. For astrophysical and other applications, this model can be adjusted simply to provide isotopologue-specific cross sections for a range of relevant temperatures.

Predissociation of the B Σu-3 state of S2: A coupled-channel model.

A coupled-channel Schrödinger equation model of predissociation in the B Σu-3 state of S2 is developed and optimized by comparison with recent photoabsorption spectra of the B Σu-3-X Σg-3(v,0) bands for 11 ≤ v ≤ 27, covering the energy range 35 800-41 500 cm-1. All bands in this range exhibit varying degrees of diffuseness, with corresponding predissociation linewidths Γ ≈ 4-60 cm-1 full-width at half-maximum. Model comparisons with both low-temperature (T = 370 K) and high-temperature (T = 823 K) spectra indicate, for many bands, significant dependence of the linewidth on both the rotational quantum number J and the fine-structure component Fi. Just as in the analogous case of O2, the B(v)-state predissociation in S2 is caused principally by spin-orbit interaction with 3Πu, 1Πu, 5Πu, and Σu+3 states. The inner-limb crossing with B″3Πu is responsible for the predissociation of B(v = 11) and provides a significant slowly varying contribution for B(v ≥ 12). The outer crossings with the 1Πu, 5Πu, and 2 Σu+3 states are responsible for oscillatory contributions to the predissociation widths, with first peaks at v = 13, 20, and 24, respectively, and the 5Πu contribution dominant. Prior to the photodissociation imaging study of Frederix et al. [J. Phys. Chem. A 113, 14995 (2009)], which redefined the dissociation energy of S2, the prevailing paradigm was that only the 1Πu interaction was responsible for the B(v = 11-16) predissociation: this view is not supported by our model.

NOO Peroxy Isomer Exposed with Velocity-Map Imaging.

The chemistry of NO2, a key atmospheric trace gas, has historically been interpreted in terms of the C2v isomer ONO, with the peroxy isomer NOO only postulated to be stable. In this work, a velocity-map-imaged photoelectron spectrum of the nitrite anion, NO2-, reveals energetic-electron structure that may only occur by photodetachment from the NOO-(X̃1A') isomer. This measurement defines NOO(X̃2A') bond frequencies and an electron affinity of only 335(30) cm-1, which, supported by ab initio calculations, confirm the first observation of this important reactive species.

Re-shaping NHS orthodontic provision - the North Wales experience.

The orthodontic service provision within North Wales, in common with many areas of the United Kingdom, was experiencing increasing waiting times for assessment and treatment. Reasons for this included an increasing population, patient demand and fixed NHS contracted orthodontic provision. In addition to these universal challenges, the geography of North Wales contributed to difficulties in accessing care. It was felt that with a reshaping of the orthodontic services there was potential to enhance the quality of orthodontic care available to patients and deliver prudent NHS orthodontic services. Three distinct, but inter-related steps, were identified to progress the reshaping of the service with the intended outcome of achieving an improved co-ordinated service. Initially, this involved the re-commissioning of the primary care specialist service through a formal retendering process. Following this, a standardised orthodontic referral form was developed, to be used for all orthodontic referrals regardless of whether their destination was a primary or secondary care provider. Finally, a formal accreditation process for all non-specialist dentists who were undertaking NHS orthodontic treatment was developed and implemented. The successful outcome of this process was only possible because of the close working partnership between the North Wales Orthodontic Managed Clinical Network (OMCN) and Betsi Cadwaladr University Health Board.

Do incident and recurrent venous thromboembolism risks truly differ between heterozygous and homozygous Factor V Leiden carriers? A retrospective cohort study.

INTRODUCTION: While Factor V Leiden (F5 rs6025 A allele) is a known venous thromboembolism (VTE) risk factor, VTE risk among heterozygous vs. homozygous carriers is uncertain. MATERIALS AND METHODS: In a retrospective cohort study of Mayo Clinic patients referred for genotyping between 1996 and 2013, we tested Factor V Leiden genotype as a risk factor for incident and recurrent VTE. RESULTS: Among heterozygous (n=268) and homozygous (n=111) carriers, the prevalence of VTE was 54% and 68%, respectively (p=0.016). While mean patient age at first VTE event (43.9 vs. 42.9years; p=0.70) did not differ significantly, median VTE-free survival was modestly shorter for homozygous carriers (56.8 vs 59.5 years; p=0.04). Sixty-nine (48%) and 31 (42%) heterozygous and homozygous carriers had ≥1 VTE recurrence (p=0.42). In a multivariable model, idiopathic incident VTE and a second thrombophilia were associated with increased and anticoagulation duration >6months with reduced hazards of VTE recurrence; Factor V Leiden genotype was not an independent predictor of recurrence. CONCLUSIONS: Aside from a higher VTE prevalence and modestly reduced VTE-free survival, VTE penetrance and phenotype severity did not differ significantly among homozygous vs. heterozygous carriers, suggesting that VTE prophylaxis and management should not differ by Factor V Leiden genotype.

Observation of a new electronic state of CO perturbing W ¹Π(v=1).

We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

The design and development of surgical templates for premolar transplants in adolescents.

The aim of designing and fabricating the surgical templates was to assist the surgical component of premolar transplantation, by establishing and replicating the root dimensions of the donor premolar tooth. The correct template could be used to assess the socket preparation (width and depth) prior to placement of the transplant in the recipient site, obviating the need to repeatedly try the donor tooth for fit at the recipient site, thereby minimising trauma to the periodontal ligament of the donor tooth. Seventy-five mandibular premolars and 50 maxillary second premolars were selected with varying stages of root development. All teeth had been extracted for orthodontic reasons. The root was measured for its length (maxL) and maximum (maxW) and minimum width (minW) with digital callipers from standardised reference points. These measurements were then used in the design of premolar transplant templates. The mean measurements for second maxillary premolars were maxL 14.6 mm (± 1.7), maxW 8.3 mm (± 0.5) and minW 4.9 (± 0.3). The mean measurements for mandibular premolars were maxL 14.8 (± 1.6), maxW 7.4 (± 0.6) and minW 5.3 (± 0.5). From these measurements, a range of maxillary second premolar and mandibular premolar templates have been fabricated. These figures also inform the multidisciplinary planning process for the space requirements at the donor site prior to transplantation.

High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions: the electron affinity of CS2.

A combination of high-resolution velocity-map-imaging photoelectron spectroscopy and isotopic substitution is used to show that precise electron affinities can be obtained from polyatomic photodetachment spectra, even for cases involving significant changes in equilibrium geometry between the molecular neutral and anion. The chosen example CS(2) (X (1)Σ(g)(+)) (linear) ← CS(2)(-) (X (2)A(1)) (bent) photodetachment transition is found to preferentially access highly-excited v(2) (bending) levels of the neutral, with no observation possible of the lowest-v(2) bands. Nevertheless, through (13)C isotopic substitution, the v(2) numbering is established unambiguously and the adiabatic electron affinity of CS(2) is found to be 4456(10) cm(-1) [0.5525(13) eV], by far the most precise value reported to date.

Experimental verification of strong rotational dependence of fluorescence and predissociation yield in the b1Πu(v = 1) level of 14N2.

New, rotationally resolved fluorescence-excitation spectra confirm coupled-channel Schrödinger-equation predictions of strong rotational dependence of the fluorescence and predissociation yields in the b(v = 1) level of (14)N(2).

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N.

The first comprehensive high-resolution photoabsorption spectrum of (14)N(15)N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm(-1) (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N(2) that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schrödinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

Oscillator strengths and line widths of dipole-allowed transitions in (14)N2 between 86.0 and 89.7 nm.

Oscillator strengths of 23 electric-dipole-allowed bands of (14)N(2) in the 86.0-89.7 nm (111,480-116,280 cm(-1)) region are reported from synchrotron-based photoabsorption measurements at an instrumental resolution of 6.5x10(-4) nm (0.7 cm(-1)) full width at half maximum. The absorption spectrum comprises transitions to vibrational levels of the c(n) (1)Pi(u) (n=3,4), o(3) (1)Pi(u), and c(n+1)(') (1)Sigma(u)(+)(n=3,4) Rydberg states as well as the b (1)Pi(u) and b(') (1)Sigma(u)(+) valence states. The J dependences of band f-values derived from the experimental line f-values are reported as polynomials in J(J+1) and are extrapolated to zero nuclear rotation in order to facilitate comparisons with the results of coupled Schrodinger equation calculations. Many bands in this study are characterized by a strong J dependence of the band f-values and display anomalous P-, Q-, and R-branch intensity patterns. Predissociation line widths are reported for six bands. The experimental f-value and line-width patterns inform current efforts to develop comprehensive spectroscopic models for N(2) that incorporate rotational effects and predissociation mechanisms, and are critical for the construction of realistic atmospheric radiative-transfer models.

Optical observation of the C, 3ssigma(g)F3, and 3ppi(u)G3 3Pi(u) states of N2.

High-resolution laser-based one extreme-ultraviolet (EUV)+one UV two-photon ionization spectroscopy and EUV photoabsorption spectroscopy have been employed to study spin-forbidden (3)Pi(u)-X (1)Sigma(g) (+)(v,0) transitions in (14)N(2) and (15)N(2). Levels of the C (3)Pi(u) valence and 3ssigma(g)F(3) and 3ppi(u)G(3) (3)Pi(u) Rydberg states are characterized, either through their direct optical observation, or, indirectly, through their perturbative effects on the (1)Pi(u) and (1)Sigma(u) (+) states, which are accessible in dipole-allowed transitions. Optical observation of the G(3)-X(0,0) and (1,0) transitions is reported for the first time, together with evidence for six new vibrational levels of the C state. Following the recent observation of the F(3)-X(0,0) transition at rotational resolution [J. P. Sprengers et al., J. Chem. Phys. 123, 144315 (2005)], the F(3)(v=1) level is found to be responsible for a local perturbation in the rotational predissociation pattern of the b(') (1)Sigma(u) (+)(v=4) state. Despite their somewhat fragmentary nature, these new observations provide a valuable database on the (3)Pi(u) states of N(2) and their interactions which will help elucidate the predissociation mechanisms for the nitrogen molecule.

A coupled-channel model of the 3Pi(u) states of N2: structure and interactions of the 3ssigma(g)F3 3Pi(u) and 3ppi(u)G3 3Pi(u) Rydberg states.

New and existing spectroscopic data on N(2), obtained using a wide variety of experimental techniques, are interpreted using a coupled-channel Schrodinger-equation (CSE) model of the structure and predissociation dynamics for the interacting Rydberg and valence states of (3)Pi(u) symmetry. As a result, v>0 levels of the 3ppi(u)G(3) (3)Pi(u) Rydberg state are assigned correctly for the first time, leading to the identification of very strong perturbations in the G(3)-state vibrational structure. A four-channel CSE model, which includes the 3ssigma(g)F(3) (3)Pi(u) and 3ppi(u)G(3) (3)Pi(u) Rydberg states and the C(') (3)Pi(u) and C (3)Pi(u) valence states, indicates strong Rydberg-Rydberg coupling between the F(3) and G(3) states, strong Rydberg-valence coupling between the G(3) and C(') states, and weaker coupling between the F(3) and C(') states.

Sign reversal of the spin-orbit constant for the C 3Pi(u) state of N2.

Ab initio calculations are performed at the multireference configuration-interaction level of theory on the diagonal spin-orbit functions for the lowest non-Rydberg states of (3)Pi(u) symmetry in molecular nitrogen. Spin-orbit constants deduced from the ab initio results confirm the recent suggestion, based on new experimental results, that the C (3)Pi(u) state of N(2), long known to be regular in the region of its potential-energy curve minimum, becomes inverted at higher energies. By removing the effects of the crossing C(') (3)Pi(u) state, it is shown that A(v) for the C state changes sign from positive to negative near v=8, corresponding to a change in principal molecular-orbital configuration from (1sigma(g))(2)(1sigma(u))(2)(2sigma(g))(2)(2sigma(u))(3sigma(g))(2)(1pi(u))(4)(1pi(g)) to (1sigma(g))(2)(1sigma(u))(2)(2sigma(g))(2)(2sigma(u))(2)(3sigma(g))(1pi(u))(3)(1pi(g))(2) at an internuclear distance near 1.4 A.

Structure and predissociation of the 3psigma(u)D (3)Sigma(u) (+) Rydberg state of N(2): first extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis.

The 3psigma(u)D (3)Sigma(u) (+) Rydberg state of N(2) is studied experimentally using two high-resolution spectroscopic techniques. First, the forbidden D (3)Sigma(u) (+)-X (1)Sigma(g) (+) transition is observed for the first time via the (0,0) band of (14)N(2) and the (1,0) band of (15)N(2), using 1 extreme-ultraviolet +1 ultraviolet two-photon-ionization laser spectroscopy. Second, the Rydberg-Rydberg transition D (3)Sigma(u) (+)-E (3)Sigma(g) (+) is studied using near-infrared diode-laser photoabsorption spectroscopy, thus extending the previous measurements of Kanamori et al. [J. Chem. Phys. 95, 80 (1991)], to higher transition energies, and thereby revealing the (2,2) and (3,3) bands. The combined results show that the D(v=0-3) levels exhibit rapidly increasing rotational predissociation as v increases, spanning nearly four orders of magnitude. The D-state level structure and rotational predissociation signature are explained by means of a coupled-channels model which considers the electrostatically coupled (3)Pi(u) Rydberg-valence manifold, together with a pure-precession L-uncoupling rotational interaction between the 3psigma(u)D (3)Sigma(u) (+) and 3ppi(u)G (3)Pi(u) Rydberg p-complex components.

Interactions of the 3ppi u c1Pi u(v=2) Rydberg-complex member in isotopic N2.

The 3ppi u c1Pi u-X 1Sigmag+(2,0) Rydberg and b' 1Sigmau+-X 1Sigmag+(7,0) valence transitions of 14N2, 14N15N, and 15N2 are studied using laser-based 1 extreme ultraviolet (XUV)+1' UV two-photon-ionization spectroscopy, supplemented by synchrotron-based hotoabsorption measurements in the case of 14N2. For each isotopomer, effective rotational interactions between the c(v=2) and b'(v=7) levels are found to cause strong Lambda-doubling in c(v=2) and dramatic P/R-branch intensity anomalies in the b'-X(7,0) band due to the effects of quantum interference. Local perturbations in energy and predissociation line width for the c(v=2) Rydberg level are observed and attributed to a spin-orbit interaction with the crossing, short-lived C 3Pi u(v=17) valence level.

Oscillator strengths and line widths of dipole-allowed transitions in (14)N(2) between 89.7 and 93.5 nm.

Line oscillator strengths in the 20 electric dipole-allowed bands of (14)N(2) in the 89.7-93.5 nm (111480-106950 cm(-1)) region are reported from photoabsorption measurements at an instrumental resolution of approximately 6 mA (0.7 cm(-1)) full width at half maximum. The absorption spectrum comprises transitions to vibrational levels of the 3p sigma(u) c(4)' (1)Sigma(u)(+), 3p pi(u) c(3) (1)Pi(u), and 3s sigma(g) o(3) (1)Pi(u) Rydberg states and of the b' (1)Sigma(u)(+) and b (1)Pi(u) valence states. The J dependences of band f values derived from the experimental line f values are reported as polynomials in J'(J'+1) and are extrapolated to J'=0 in order to facilitate comparisons with results of coupled Schrodinger-equation calculations. Most bands in this study are characterized by a strong J dependence of the band f values and display anomalous P-, Q-, and R-branch intensity patterns. Predissociation line widths, which are reported for 11 bands, also exhibit strong J dependences. The f value and line width patterns can inform current efforts to develop comprehensive spectroscopic models that incorporate rotational effects and predissociation mechanisms, and they are critical for the construction of realistic atmospheric radiative-transfer models.