The Diamine Cation Is Not a Chemical Example Where Density Functional Theory Fails

In a recent communication, Weber and co-workers presented a surprising study on charge-localization effects in the N,N'-dimethylpiperazine (DMP+) diamine cation to provide a stringent test of density functional theory (DFT) methods. Within their study, the authors examined various DFT methods and concluded that "all DFT functionals commonly used today, including hybrid functionals with exact exchange, fail to predict a stable charge-localized state." This surprising conclusion is based on the authors' use of a self-interaction correction (namely, complex-valued Perdew-Zunger Self-Interaction Correction (PZ-SIC)) to DFT, which appears to give excellent agreement with experiment and other wavefunction-based benchmarks. Since the publication of this recent communication, the same DMP+ molecule has been cited in numerous subsequent studies as a prototypical example of the importance of self-interaction corrections for accurately calculating other chemical systems. In this correspondence, we have carried out new high-level CCSD(T) analyses on the DMP+ cation to show that DFT actually performs quite well for this system (in contrast to their conclusion that all DFT functionals fail), whereas the PZ-SIC approach used by Weber et al. is the outlier that is inconsistent with the high-level CCSD(T) (coupled-cluster with single and double excitations and perturbative triples) calculations. Our new findings and analysis for this system are briefly discussed in this correspondence.Comment: Accepted by Nature Communication

Analysis of Flexural Strength and Contact Pressure After Simulated Chairside Adjustment of Pressed Lithium Disilicate Glass-Ceramic

Statement of problem Research evaluating load-to-failure of pressed lithium disilicate glass-ceramic (LDGC) with a clinically validated test after adjustment and repair procedures is scarce. Purpose The purpose of this in vitro study was to investigate the effect of the simulated chairside adjustment of the intaglio surface of monolithic pressed LDGC and procedures intended to repair damage. Material and methods A total of 423 IPS e.max Press (Ivoclar Vivadent AG) disks (15 mm diameter, 1 mm height) were used in the study. The material was tested by using an equibiaxial loading arrangement (n≥30/group) and a contact pressure test (n≥20/group). Specimens were assigned to 1 of 14 groups. One-half was assigned to the equibiaxial load test and the other half underwent contact pressure testing. Testing was performed in 2 parts, before glazing and after glazing. Before-glazing specimens were devested and entered in the test protocol, while after-glazing specimens were devested and glazed before entering the test protocol. Equibiaxial flexure test specimens were placed on a ring-on-ring apparatus and loaded until failure. Contact pressure specimens were cemented to epoxy resin blocks with a resin cement and loaded with a 50-mm diameter hemisphere until failure. Tests were performed on a universal testing machine with a crosshead speed of 0.5 mm/min. Weibull statistics and likelihood ratio contour plots determined intergroup differences (95% confidence bounds). Results Before glazing, the equibiaxial flexural strength test and the Weibull and likelihood ratio contour plots demonstrated a significantly higher failure strength for 1EC (188 MPa) than that of the damaged and/or repaired groups. Glazing following diamond-adjustment (1EGG) was the most beneficial post-damage procedure (176 MPa). Regarding the contact pressure test, the Weibull and likelihood ratio contour plots revealed no significant difference between the 1PC (98 MPa) and 1PGG (98 MPa) groups. Diamond-adjustment, without glazing (1EG and 1PG), resulted in the next-to-lowest equibiaxial flexure strength and the lowest contact pressure. After glazing, the strength of all the groups, when subjected to glazing following devesting, increased in comparison with corresponding groups in the before-glazing part of the study. Conclusions A glazing treatment improved the mechanical properties of diamond-adjusted IPS e.max Press disks when evaluated by equibiaxial flexure and contact pressure tests. Clinical Implications When adjustments are made on the intaglio surface of a pressed lithium disilicate glass-ceramic, a subsequent glazing treatment is recommended to improve strength

Perturbative Analysis of Spectral Singularities and Their Optical Realizations

We develop a perturbative method of computing spectral singularities of a Schreodinger operator defined by a general complex potential that vanishes outside a closed interval. These can be realized as zero-width resonances in optical gain media and correspond to a lasing effect that occurs at the threshold gain. Their time-reversed copies yield coherent perfect absorption of light that is also known as an antilaser. We use our general results to establish the exactness of the n-th order perturbation theory for an arbitrary complex potential consisting of n delta-functions, obtain an exact expression for the transfer matrix of these potentials, and examine spectral singularities of complex barrier potentials of arbitrary shape. In the context of optical spectral singularities, these correspond to inhomogeneous gain media.Comment: 13 pages, 2 figures, one table, a reference added, typos correcte

General Lower Bounds for b -> d Penguin Processes

For the exploration of flavour physics, b -> d penguin processes are an important aspect, with the prominent example of \bar B^0_d -> K^0 \bar K^0. We recently derived lower bounds for the CP-averaged branching ratio of this channel in the Standard Model; they were found to be very close to the corresponding experimental upper limits, thereby suggesting that \bar B^0_d -> K^0 \bar K^0 should soon be observed. In fact, the BaBar collaboration subsequently announced the first signals of this transition. Here we point out that it is also possible to derive lower bounds for \bar B -> \rho \gamma decays, which are again surprisingly close to the current experimental upper limits. We show that these bounds are realizations of a general bound that holds within the Standard Model for b -> d penguin processes, allowing further applications to decays of the kind B^\pm -> K^{(\ast)\pm} K^{(\ast)} and B^\pm -> \pi^\pm \ell^+ \ell^-, \rho^\pm \ell^+ \ell^-.Comment: Minor changes, to appear as rapid communication in Phys. Rev

A Physical Realization of the Generalized PT-, C-, and CPT-Symmetries and the Position Operator for Klein-Gordon Fields

Generalized parity (P), time-reversal (T), and charge-conjugation (C)operators were initially definedin the study of the pseudo-Hermitian Hamiltonians. We construct a concrete realization of these operators for Klein-Gordon fields and show that in this realization PT and C operators respectively correspond to the ordinary time-reversal and charge-grading operations. Furthermore, we present a complete description of the quantum mechanics of Klein-Gordon fields that is based on the construction of a Hilbert space with a relativistically invariant, positive-definite, and conserved inner product. In particular we offer a natural construction of a position operator and the corresponding localized and coherent states. The restriction of this position operator to the positive-frequency fields coincides with the Newton-Wigner operator. Our approach does not rely on the conventional restriction to positive-frequency fields. Yet it provides a consistent quantum mechanical description of Klein-Gordon fields with a genuine probabilistic interpretation.Comment: 20 pages, published versio

Specific recognition of a multiply phosphorylated motif in the DNA repair scaffold XRCC1 by the FHA domain of human PNK.

Short-patch repair of DNA single-strand breaks and gaps (SSB) is coordinated by XRCC1, a scaffold protein that recruits the DNA polymerase and DNA ligase required for filling and sealing the damaged strand. XRCC1 can also recruit end-processing enzymes, such as PNK (polynucleotide kinase 3'-phosphatase), Aprataxin and APLF (aprataxin/PNK-like factor), which ensure the availability of a free 3'-hydroxyl on one side of the gap, and a 5'-phosphate group on the other, for the polymerase and ligase reactions respectively. PNK binds to a phosphorylated segment of XRCC1 (between its two C-terminal BRCT domains) via its Forkhead-associated (FHA) domain. We show here, contrary to previous studies, that the FHA domain of PNK binds specifically, and with high affinity to a multiply phosphorylated motif in XRCC1 containing a pSer-pThr dipeptide, and forms a 2:1 PNK:XRCC1 complex. The high-resolution crystal structure of a PNK-FHA-XRCC1 phosphopeptide complex reveals the basis for this unusual bis-phosphopeptide recognition, which is probably a common feature of the known XRCC1-associating end-processing enzymes

Teaching percutaneous renal biopsy using unfixed human cadavers

Background: Percutaneous renal biopsy (PRB) is an important diagnostic procedure. Despite advances in its safety profile there remains a small but significant risk of bleeding complications. Traditionally, operators train to perform PRB through tutor instruction and directly supervised PRB attempts on real patients. We describe an approach to teaching operators to perform PRB using cadaveric simulation. Methods: We devised a full day course hosted in the Clinical Anatomy Skills Centre, with places for nine candidates. Course faculty consisted of two Consultant Nephrologists, two Nephrology trainees experienced in PRB, and one Radiologist. Classroom instruction included discussion of PRB indications, risk minimisation, and management of complications. Two faculty members acted as models for the demonstration of kidney localisation using real-time ultrasound scanning. PRB was demonstrated using a cadaveric model, and candidates then practised PRB using each cadaver model. Results: Written candidate feedback was universally positive. Faculty considered the cadaveric model a realistic representation of live patients, while the use of multiple cadavers introduced anatomical variation. Conclusions: Our model facilitates safe simulation of a high risk procedure. This might reduce serious harm associated with PRB and improve patient safety, benefiting trainee operators and patients alike

Entropy Bound with Generalized Uncertainty Principle in General Dimensions

In this letter, the entropy bound for local quantum field theories (LQFT) is studies in a class of models of the generalized uncertainty principle(GUP) which predicts a minimal length as a reflection of the quantum gravity effects. Both bosonic and fermionic fields confined in arbitrary spatial dimension $d\geq4$ ball ${\cal B}^{d}$ are investigated. It is found that the GUP leads to the same scaling $A_{d-2}^{(d-3)/(d-2)}$ correction to the entropy bound for bosons and fermions, although the coefficients of this correction are different for each case. Based on our calculation, we conclude that the GUP effects can become manifest at the short distance scale. Some further implications and speculations of our results are also discussed.Comment: 8 pages, topos corrected and references adde