Theory of x-ray scattering from laser-driven electronic systems

We describe, within the framework of quantum electrodynamics, an interaction between a non-resonant hard x-ray pulse and an electronic system in the presence of a temporally periodic laser field driving electron dynamics in this system. We apply Floquet theory to describe the laser-driven electronic system, and then obtain the scattering probability of an arbitrary nonresonant x-ray pulse from such a system employing the density-matrix formalism. We show that the scattering probability can be connected to the time-dependent electron density of the driven electronic system only under certain conditions, in particular, if the bandwidth of the probe x-ray pulse is sufficiently narrow to spectroscopically resolve transitions to different final states. A special focus is laid on application of the theory to laser-driven crystals in a strongly nonperturbative regime. We show how the time-dependent electron density of a crystal can be reconstructed from energy-resolved scattering patterns. This is illustrated by a calculation of a diffraction signal from a driven MgO crystal.Comment: accepted to Phys Rev

To Wet or Not to Wet? Dispersion Forces Tip the Balance for Water Ice on Metals

Despite widespread discussion, the role of van der Waals dispersion forces in wetting remains unclear. Here we show that nonlocal correlations contribute substantially to the water-metal bond and that this is an important factor in governing the relative stabilities of wetting layers and 3D bulk ice. Because of the greater polarizability of the substrate metal atoms, nonlocal correlations between water and the metal exceed those between water molecules within ice. This sheds light on a long-standing problem, wherein common density functional theory exchange-correlation functionals incorrectly predict that none of the low temperature experimentally characterized icelike wetting layers are thermodynamically stable

Proteostasis collapse is a driver of cell aging and death.

What molecular processes drive cell aging and death? Here, we model how proteostasis-i.e., the folding, chaperoning, and maintenance of protein function-collapses with age from slowed translation and cumulative oxidative damage. Irreparably damaged proteins accumulate with age, increasingly distracting the chaperones from folding the healthy proteins the cell needs. The tipping point to death occurs when replenishing good proteins no longer keeps up with depletion from misfolding, aggregation, and damage. The model agrees with experiments in the worm Caenorhabditis elegans that show the following: Life span shortens nonlinearly with increased temperature or added oxidant concentration, and life span increases in mutants having more chaperones or proteasomes. It predicts observed increases in cellular oxidative damage with age and provides a mechanism for the Gompertz-like rise in mortality observed in humans and other organisms. Overall, the model shows how the instability of proteins sets the rate at which damage accumulates with age and upends a cell's normal proteostasis balance

Absolute frequency measurement of the 7s2^2 1^1S0_0 −- 7s7p 1^{1}P1_1 transition in 225^{225}Ra

Transition frequencies were determined for transitions in Ra in an atomic beam and for reference lines in Te$_2$ molecules in a vapor cell. The absolute frequencies were calibrated against a GPS stabilized Rb-clock by means of an optical frequency comb. The 7s^2\,^1S$_0$(F = 1/2)-7s7p\,^1P$_1$(F = 3/2) transition in $^{225}$Ra was determined to be $621\,042\,124(2)\,$MHz. The measurements provide input for designing efficient and robust laser cooling of Ra atoms in preparation of a search for a permanent electric dipole moment in Ra isotopes.Comment: Accepted for publication in the rapid communication of Physical review

Local Structure Analysis in AbAb InitioInitio Liquid Water

Within the framework of density functional theory, the inclusion of exact exchange and non-local van der Waals/dispersion (vdW) interactions is crucial for predicting a microscopic structure of ambient liquid water that quantitatively agrees with experiment. In this work, we have used the local structure index (LSI) order parameter to analyze the local structure in such highly accurate $ab$ $initio$ liquid water. At ambient conditions, the LSI probability distribution, P($I$), was unimodal with most water molecules characterized by more disordered high-density-like local environments. With thermal excitations removed, the resultant bimodal P($I$) in the inherent potential energy surface (IPES) exhibited a 3:1 ratio between high- and low-density-like molecules, with the latter forming small connected clusters amid the predominant population. By considering the spatial correlations and hydrogen bond network topologies $among$ water molecules with the same LSI identities, we demonstrate that the signatures of the experimentally observed low- (LDA) and high-density (HDA) amorphous phases of ice are present in the IPES of ambient liquid water. Analysis of the LSI autocorrelation function uncovered a persistence time of $\sim$ 4 ps---a finding consistent with the fact that natural thermal fluctuations are responsible for transitions between these distinct yet transient local aqueous environments in ambient liquid water.Comment: 12 pages, 6 figure

Thermal Expansion in Dispersion-Bound Molecular Crystals

We explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with $ab$ $initio$ molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridine-like molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I ($\approx 40$% more than classical thermal expansion at $153$ K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. When predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and sophisticated treatments of Pauli repulsion are needed in dispersion-bound molecular crystals

Stochastic Multifacility Location Problem under Triangular Area Constraint with Euclidean Norm

The multifacility location issue is an augmentation of the single-location problem in which we might be keen on finding the location of various new facilities concerning different existing locations. In the present study, multifacility location under triangular zone limitation with probabilistic methodology for the weights considered in the objective function and the Euclidean distances between the locations has been presented. Scientific detailing and the explanatory arrangement have been acquired by utilizing Kuhn-Tucker conditions. The arrangement strategy has been represented with the assistance of a numerical illustration. Two sub-instances of the issue in each of which the new locations are to be situated in semi-open rectangular zone have likewise been talked about

On how good DFT exchange-correlation functionals are for H bonds in small water clusters: Benchmarks approaching the complete basis set limit

The ability of several density-functional theory (DFT) exchange-correlation functionals to describe hydrogen bonds in small water clusters (dimer to pentamer) in their global minimum energy structures is evaluated with reference to second order Moeller Plesset perturbation theory (MP2). Errors from basis set incompleteness have been minimized in both the MP2 reference data and the DFT calculations, thus enabling a consistent systematic evaluation of the true performance of the tested functionals. Among all the functionals considered, the hybrid X3LYP and PBE0 functionals offer the best performance and among the non-hybrid GGA functionals mPWLYP and PBE1W perform the best. The popular BLYP and B3LYP functionals consistently underbind and PBE and PW91 display rather variable performance with cluster size.Comment: 9 pages including 4 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

An integrated water balance model for assessing water scarcity in a data-sparse interfluve in Eastern India

The objective of this study is to measure the balance of water demand versus water resource availability in an interfluve of West Bengal, India to support water resource planning, particularly of inter-basin transfers. Surface water availability was modelled using the Soil Conservation Service Curve Number (SCS-CN) model, whilst groundwater availability was modelled based on water level fluctuations and the rainfall infiltration method. Water use was modelled separately for the agricultural, industrial, and domestic sectors using a predominantly normative approach and water use to availability ratios calculated for different administrative areas within the interfluve. Overall, the approach suggested that the interfluve receives 327×106m3year?1 of excess water after satisfying these sectoral demands, but that the eastern part of the study area is in deficit. However, a sensitivity analysis carried on the approach to several assumptions in the model suggested changed circumstances would produce surplus/deficit ranging from -215×106m3year?1 to 435 ×106m3year?1 . The approach could have potential for localised water balance modelling in other Indian catchment