697 research outputs found
Exact two-component TDDFT with simple two-electron picture-change corrections: X-ray absorption spectra near L- and M-edges of four-component quality at two-component cost
X-ray absorption spectroscopy (XAS) has gained popularity in recent years as it probes matter with high spatial and elemental sensitivity. However, the theoretical modelling of XAS is a challenging task since XAS spectra feature a fine structure due to scalar (SC) and spin-orbit (SO) relativistic effects, in particular near L and M absorption edges. While full four-component (4c) calculations of XAS are nowadays feasible, there is still interest in developing approximate relativistic methods that enable XAS calculations at the two-component (2c) level while maintaining the accuracy of the parent 4c approach. In this article we present theoretical and numerical insights into two simple yet accurate 2c approaches based on an (extended) atomic mean-field exact two-component Hamiltonian framework, (e)amfX2C, for the calculation of XAS using linear eigenvalue and damped-response time-dependent density functional theory (TDDFT). In contrast to the commonly used one-electron X2C (1eX2C) Hamiltonian, both amfX2C and eamfX2C account for the SC and SO two-electron and exchange-correlation picture-change (PC) effects that arise from the X2C transformation. As we demonstrate on L- and M-edge XAS spectra of transition metal and actinide compounds, the absence of PC corrections in the 1eX2C approximation results in a substantial overestimatation of SO splittings, whereas (e)amfX2C Hamiltonians reproduce all essential spectral features such as shape, position, and SO splitting of the 4c references in excellent agreement, while offering significant computational savings. Therefore, the (e)amfX2C PC correction models presented here constitute reliable relativistic 2c quantum-chemical approaches for modelling XAS
Accurate Relativistic Real-Time TDDFT for Valence and Core Attosecond Transient Absorption Spectroscopy
Attosecond pump-probe transient absorption spectroscopy (TAS) has opened the possibility to study pure electron dynamics on its natural time scale. However, due to the out-of-equilibrium nature of the process, first-principle theoretical modelling remains a challenging task, specially for heavy elements and/or core excitations where relativistic corrections become imperative, as the spectra contain significant imprints of both scalar and spin-orbit relativistic effects. To alleviate this problem, we formulated a methodology for computing TAS spectrum within the relativistic real-time time-dependent density functional theory (RT-TDDFT) framework, for both the valence and core energy regime. Even though RT simulations using full four-component (4c) method are feasible, they are still computationally expensive, especially for TAS. Therefore, in addition to the 4c approach, we have introduced the atomic mean-field exact two-component (amfX2C) Hamiltonian for RT-TDDFT, which accounts for one- and two-electron picture-change corrections and preserves the accuracy of the parent 4c method but at a fraction of its computational cost. Finally, we apply the amfX2C approach to study valence and near L 2,3 -edge TAS processes of experimentally relevant systems, providing additional physical insights through the lens of non-equilibrium response theory
Spatial-temporal variation in Greenland shark (Somniosus microcephalus) bycatch in the NAFO Regulatory Area
Spatial and temporal variation in Greenland shark (Somniosus microcephalus) bycatch occurrence was investigated using At-Sea Fisheries Observer data and MaxEnt, a maximum entropy species distribution model. Within the Northwest Atlantic Fisheries Organization Regulatory Area (NRA), the Flemish Pass, the slopes of the Flemish cap, and the shelf edge of Divisions 3NO contained areas of suitable habitat where Greenland shark bycatch is expected to occur. However, it should be noted that there are major areas of Greenland shark bycatch outside the NRA, in the Canadian and Greenland Exclusive Economic Zones (EEZ).En prens
The role of electronic correlation in the Si(100) reconstruction: a quantum Monte Carlo study
Recent low-temperature scanning tunneling experiments have challenged the
generally accepted picture of buckled silicon dimers as the ground state
reconstruction of the Si(100) surface. Together with the symmetric dimer model
of the surface suggested by quantum chemistry calculations on small clusters,
these findings question our general understanding of electronic correlations at
surfaces and its proper description within density functional theory. We
present quantum Monte Carlo calculations on large cluster models of the
symmetric and buckled surface, and conclude that buckling remains energetically
more favorable even when the present-day best treatment of electronic
correlation is employed.Comment: 5 pages, Revtex, 10 figure
In vivo binding of active heat shock transcription factor 1 to human chromosome 9 heterochromatin during stress
Activation of the mammalian heat shock transcription factor (HSF)1 by stress is a multistep process resulting in the transcription of heat shock genes. Coincident with these events is the rapid and reversible redistribution of HSF1 to discrete nuclear structures termed HSF1 granules, whose function is still unknown. Key features are that the number of granules correlates with cell ploidy, suggesting the existence of a chromosomal target. Here we show that in humans, HSF1 granules localize to the 9q11-q12 heterochromatic region. Within this locus, HSF1 binds through direct DNA–protein interaction with a nucleosome-containing subclass of satellite III repeats. HSF1 granule formation only requires the DNA binding competence and the trimerization of the factor. This is the first example of a transcriptional activator that accumulates transiently and reversibly on a chromosome-specific heterochromatic locus
Observations of Microwave Continuum Emission from Air Shower Plasmas
We investigate a possible new technique for microwave measurements of
ultra-high energy cosmic ray (UHECR) extensive air showers which relies on
detection of expected continuum radiation in the microwave range, caused by
free-electron collisions with neutrals in the tenuous plasma left after the
passage of the shower. We performed an initial experiment at the AWA (Argonne
Wakefield Accelerator) laboratory in 2003 and measured broadband microwave
emission from air ionized via high energy electrons and photons. A follow-up
experiment at SLAC (Stanford Linear Accelerator Center) in summer of 2004
confirmed the major features of the previous AWA observations with better
precision and made additional measurements relevant to the calorimetric
capabilities of the method. Prompted by these results we built a prototype
detector using satellite television technology, and have made measurements
indicating possible detection of cosmic ray extensive air showers. The method,
if confirmed by experiments now in progress, could provide a high-duty cycle
complement to current nitrogen fluorescence observations of UHECR, which are
limited to dark, clear nights. By contrast, decimeter microwave observations
can be made both night and day, in clear or cloudy weather, or even in the
presence of moderate precipitation.Comment: 15 pages, 13 figure
Radio-Frequency Measurements of Coherent Transition and Cherenkov Radiation: Implications for High-Energy Neutrino Detection
We report on measurements of 11-18 cm wavelength radio emission from
interactions of 15.2 MeV pulsed electron bunches at the Argonne Wakefield
Accelerator. The electrons were observed both in a configuration where they
produced primarily transition radiation from an aluminum foil, and in a
configuration designed for the electrons to produce Cherenkov radiation in a
silica sand target. Our aim was to emulate the large electron excess expected
to develop during an electromagnetic cascade initiated by an ultra high-energy
particle. Such charge asymmetries are predicted to produce strong coherent
radio pulses, which are the basis for several experiments to detect high-energy
neutrinos from the showers they induce in Antarctic ice and in the lunar
regolith. We detected coherent emission which we attribute both to transition
and possibly Cherenkov radiation at different levels depending on the
experimental conditions. We discuss implications for experiments relying on
radio emission for detection of electromagnetic cascades produced by ultra
high-energy neutrinos.Comment: updated figure 10; fixed typo in equation 2.2; accepted by PR
Antitumor activity and safety of the PARP inhibitor rucaparib in patients with high grade ovarian carcinoma and a germline or somatic BRCA1 or BRCA2 mutation: integrated analysis of data from Study 10 and ARIEL2
Objective:
An integrated analysis was undertaken to characterize the antitumor activity and safety profile of the oral poly(ADP-ribose) polymerase inhibitor rucaparib in patients with relapsed high-grade ovarian carcinoma (HGOC).
Methods:
Eligible patients from Study 10 (NCT01482715) and ARIEL2 (NCT01891344) who received a starting dose of oral rucaparib 600 mg twice daily (BID) with or without food were included in these analyses. The integrated efficacy population included patients with HGOC and a deleterious germline or somatic BRCA1 or BRCA2 (BRCA1/2) mutation who received at least two prior chemotherapies and were sensitive, resistant, or refractory to platinum-based chemotherapy. The primary endpoint was investigator-assessed confirmed objective response rate (ORR). Secondary endpoints included duration of response (DOR) and progression-free survival (PFS). The integrated safety population included patients with HGOC who received at least one dose of rucaparib 600 mg BID, irrespective of BRCA1/2 mutation status and prior treatments.
Results:
In the efficacy population (n = 106), ORR was 53.8% (95% confidence interval [CI], 43.8–63.5); 8.5% and 45.3% of patients achieved complete and partial responses, respectively. Median DOR was 9.2 months (95% CI, 6.6–11.6). In the safety population (n = 377), the most frequent treatment-emergent adverse events (AEs) were nausea, asthenia/fatigue, vomiting, and anemia/hemoglobin decreased. The most common grade ≥ 3 treatment-emergent AE was anemia/hemoglobin decreased. Treatment-emergent AEs led to treatment interruption, dose reduction, and treatment discontinuation in 58.6%, 45.9%, and 9.8% of patients, respectively. No treatment-related deaths occurred.
Conclusions:
Rucaparib has antitumor activity in advanced BRCA1/2-mutated HGOC and a manageable safety profile
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