Understanding polaritonic chemistry from ab initio quantum electrodynamics

In this review we present the theoretical foundations and first principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime. Having a rigorous and fully quantized description of interacting photons, electrons and nuclei/ions, from weak to strong light-matter coupling regimes, is pivotal for a detailed understanding of the emerging fields of polaritonic chemistry and cavity materials engineering. The use of rigorous first principles avoids ambiguities and problems stemming from using approximate models based on phenomenological descriptions of light, matter and their interactions. By starting from fundamental physical and mathematical principles, we first review in great detail non-relativistic QED, which allows to study polaritonic systems non-perturbatively by solving a Schrödinger-type equation. The resulting Pauli-Fierz quantum field theory serves as a cornerstone for the development of computational methods, such as quantum-electrodynamical density functional theory, QED coupled cluster or cavity Born-Oppenheimer molecular dynamics. These methods treat light and matter on equal footing and have the same level of accuracy and reliability as established methods of computational chemistry and electronic structure theory. After an overview of the key-ideas behind those novel ab initio QED methods, we explain their benefits for a better understanding of photon-induced changes of chemical properties and reactions. Based on results obtained by ab initio QED methods we identify the open theoretical questions and how a so far missing mechanistic understanding of polaritonic chemistry can be established. We finally give an outlook on future directions within polaritonic chemistry and first principles QED and address the open questions that need to be solved in the next years both from a theoretical as well as experimental viewpoint

Exact Solution for A Real Polaritonic System Under Vibrational Strong Coupling in Thermodynamic Equilibrium: Absence of Zero Temperature and Loss of Light-Matter Entanglement

The first exact quantum simulation of a real molecular system (HD+) under strong ro-vibrational coupling to a quantized optical cavity mode in thermal equilibrium is presented. Theoretical challenges in describing strongly coupled systems of mixed quantum statistics (Bosons and Fermions) are discussed and circumvented by the specific choice of our molecular system. Our exact simulations reveal the absence of a zero temperature for the strongly coupled matter and light subsystems, due to cavity induced non-equilibrium conditions. Furthermore, we explore the temperature dependency of light-matter quantum entanglement, which emerges for the groundstate, but is quickly lost already in the deep cryogenic regime, opposing predictions from phenomenological models (Jaynes-Cummings). Distillable molecular light-matter entanglement of ro-vibrational states may open interesting perspectives for quantum technological applications. Moreover, we find that the dynamics (fluctuations) of matter remains modified by the quantum nature of the thermal and vacuum field fluctuations for significant temperatures, e.g. at ambient conditions. These observations (loss of entanglement and coupling to quantum fluctuations) has far reaching consequences for the understanding and control of polaritonic chemistry and materials science, since a semi-classical theoretical description of light-matter interaction becomes feasible, but the typical canonical equilibrium assumption for the nuclear dynamics remains broken. This opens the door for quantum fluctuations induced stochastic resonance phenomena under vibrational strong coupling. A plausible theoretical mechanism to explain the experimentally observed resonance phenomena in absence of periodic driving, which have not yet been understood

Simulation of surface waves in porous media

We present a novel numerical algorithm for the simulation of seismic wave propagation in porous media, which is particularly suitable for the accurate modelling of surface wave-type phenomena. The differential equations of motion are based on Biot's theory of poro-elasticity and solved with a pseudospectral approach using Fourier and Chebyshev methods to compute the spatial derivatives along the horizontal and vertical directions, respectively. The time solver is a splitting algorithm that accounts for the stiffness of the differential equations. Due to the Chebyshev operator the grid spacing in the vertical direction is non-uniform and characterized by a denser spatial sampling in the vicinity of interfaces, which allows for a numerically stable and accurate evaluation of higher order surface wave modes. We stretch the grid in the vertical direction to increase the minimum grid spacing and reduce the computational cost. The free-surface boundary conditions are implemented with a characteristics approach, where the characteristic variables are evaluated at zero viscosity. The same procedure is used to model seismic wave propagation at the interface between a fluid and porous medium. In this case, each medium is represented by a different grid and the two grids are combined through a domain-decomposition method. This wavefield decomposition method accounts for the discontinuity of variables and is crucial for an accurate interface treatment. We simulate seismic wave propagation with open-pore and sealed-pore boundary conditions and verify the validity and accuracy of the algorithm by comparing the numerical simulations to analytical solutions based on zero viscosity obtained with the Cagniard-de Hoop method. Finally, we illustrate the suitability of our algorithm for more complex models of porous media involving viscous pore fluids and strongly heterogeneous distributions of the elastic and hydraulic material propertie

On the evaluation of plane-wave reflection coefficients in anelastic media

Analytical evaluations of the reflection coefficients in anelastic media inherently suffer from ambiguities related to the complex square roots contained in the expressions of the vertical slowness and polarization. This leads to a large number of mathematically correct but physically unreasonable solutions. To identify the physical solution, we compute full-waveform synthetic seismograms and use a frequency-slowness method for evaluating the amplitude and phase of the corresponding reflection coefficient. We perform this analysis for transversely isotropic media. The analytical solution space and its ambiguities are explored by analysing the paths along the Riemann surfaces associated with the square roots. This analysis allows us to choose the correct sign. Although this approach is generally effective, there are some cases that require an alternative solution, because the correct integration path for the vertical slowness does not exist on the corresponding Riemann surface. Closer inspection then shows that these ‘pathological' cases, which are essentially characterized by a higher-attenuation layer overlying a lower-attenuation layer, can readily be resolved through an appropriate change of direction on the Riemann sheet. The thus resulting recipe for the analytical evaluation of plane-wave reflection coefficients in anelastic media is conceptually simple and robust and provides correct solutions beyond the equivalent elastic critical (EEC) angl

A pseudospectral method for the simulation of 3-D ultrasonic and seismic waves in heterogeneous poroelastic borehole environments

We present a novel approach for the comprehensive, flexible and accurate simulation of poroelastic wave propagation in 3-D cylindrical coordinates. An important application of this method is the realistic modelling of complex seismic wave phenomena in fluid-filled boreholes, which represents a major, as of yet largely unresolved, problem in exploration geophysics. To this end, we consider a numerical mesh consisting of three concentric domains representing the borehole fluid in the centre followed by the mudcake and/or casing, and the surrounding porous formation. The spatial discretization is based on a Chebyshev expansion in the radial direction and Fourier expansions in the vertical and azimuthal directions as well as a Runge-Kutta integration scheme for the time evolution. Trigonometric interpolation and a domain decomposition method based on the method of characteristics are used to match the boundary conditions at the fluid/porous-solid and porous-solid/porous-solid interfaces as well as to reduce the number of gridpoints in the innermost domain for computational efficiency. We apply this novel modelling approach to the particularly challenging scenario of near-surface borehole environments. To this end, we compare 3-D heterogeneous and corresponding rotationally invariant simulations, assess the sensitivity of Stoneley waves to formation permeability in the presence of a casing and evaluate the effects of an excavation damage zone behind a casing on sonic log recordings. Our results indicate that only first arrival times of fast modes are reasonably well described by rotationally invariant approximations of 3-D heterogenous media. We also find that Stoneley waves are indeed remarkably sensitive to the average permeability behind a perforated PVC casing, and that the presence of an excavation damage zone behind a casing tends to dominate the overall signature of recorded seismogram

Comparing Results of Concurrent and Retrospective Designs in a Hospital Utilization Review

Hospital utilization reviews are performed on the basis of lists of explicit criteria, such as the Appropriateness Evaluation Protocol, both concurrently and retrospectively, in an increasing number of settings as part of efforts to improve the performance of hospitals and to reduce health care costs. Retrospective data collection has advantages in terms of expenses and ease of sampling, but relies on the quality of medical records. We report on a comparison between concurrent and retrospective data collection performed simultaneously and independently by two reviewers on the same hospital stays in the regional St-Loup Hospital. Results suggest that retrospective data collection produces higher rates of inappropriate hospital utilization, due to a limited number of criteria that are recorded concurrently, but are not found in the retrospective reading of medical records. These results should encourage a further investigation of the comparability between concurrent and retrospective designs in other settings. © 1997 Elsevier Science Ltd. All rights reserve

Non-invasive voiding assessment in conscious mice

OBJECTIVE: To review available options of assessing murine bladder function and to evaluate a non-invasive technique suitable for long-term recording. METHODS: We reviewed previously described methods to record rodent bladder function. We used modified metabolic cages to capture novel recording tracings of mouse micturition. We evaluated our method in a pilot study with female mice undergoing partial bladder outlet obstruction or sham operation, respectively; half of the partial obstruction and sham group received treatment with an S6K-inhibitor, targeting the mTOR pathway, which is known to be implicated in bladder response to obstruction. RESULTS: Our non-invasive method using continuous urine weight recording reliably detected changes in murine bladder function resulting from partial bladder outlet obstruction or treatment with S6K-inhibitor. We found obstruction as well as treatment with S6K-inhibitor to correlate with a hyperactive voiding pattern. CONCLUSIONS: While invasive methods to assess murine bladder function largely disturb bladder histology and intrinsically render post-cystometry gene expression analysis of questionable value, continuous urine weight recording is a reliable, inexpensive, and critically non-invasive method to assess murine bladder function, suitable for a long-term application

Ventricular pre-excitation in cats: 17 cases.

OBJECTIVES Atrioventricular accessory pathways are abnormal electrical connections between the atria and ventricles that predispose to ventricular pre-excitation (VPE) and tachycardias. ANIMALS Seventeen cats with VPE and 15 healthy matched-control cats. MATERIAL AND METHODS Multicenter case-control retrospective study. Clinical records were searched for cats with VPE, defined as preserved atrioventricular synchrony, reduced PQ interval, and increased QRS complex duration with a delta wave. Clinical, electrocardiography, echocardiographic, and outcome data were collated. RESULTS Most cats with VPE were male (16/17 cats), non-pedigree cats (11/17 cats). Median age and mean body weight were 5.4 years (0.3-11.9 years) and 4.6 ± 0.8 kg, respectively. Clinical signs at presentation included lethargy (10/17 cats), tachypnea (6/17 cats), and/or syncope (3/17 cats). In two cats, VPE was an incidental finding. Congestive heart failure was uncommon (3/17 cats). Nine (9/17) cats had tachyarrhythmias: 7/9 cats had narrow QRS complex tachycardia and 2/9 cats had wide QRS complex tachycardia. Four cats had ventricular arrhythmias. Cats with VPE had larger left (P < 0.001) and right (P < 0.001) atria and thicker interventricular septum (P = 0.019) and left ventricular free wall (P = 0.028) than controls. Three cats had hypertrophic cardiomyopathy. Treatment included different combinations of sotalol (5/17 cats), diltiazem (5/17 cats), atenolol (4/17 cats), furosemide (4/17 cats), and platelet inhibitors (4/17 cats). Five cats died, all from cardiac death (median survival time 1882 days [2-1882 days]). CONCLUSIONS Cats with VPE had a relatively long survival, albeit showing larger atria and thicker left ventricular walls than healthy cats

Inorganic pyrophosphatase in uncultivable hemotrophic mycoplasmas: identification and properties of the enzyme from Mycoplasma suis

BACKGROUND: Mycoplasma suis belongs to a group of highly specialized hemotrophic bacteria that attach to the surface of host erythrocytes. Hemotrophic mycoplasmas are uncultivable and the genomes are not sequenced so far. Therefore, there is a need for the clarification of essential metabolic pathways which could be crucial barriers for the establishment of an in vitro cultivation system for these veterinary significant bacteria.Inorganic pyrophosphatases (PPase) are important enzymes that catalyze the hydrolysis of inorganic pyrophosphate PPi to inorganic phosphate Pi. PPases are essential and ubiquitous metal-dependent enzymes providing a thermodynamic pull for many biosynthetic reactions. Here, we describe the identification, recombinant production and characterization of the soluble (s)PPase of Mycoplasma suis. RESULTS: Screening of genomic M. suis libraries was used to identify a gene encoding the M. suis inorganic pyrophosphatase (sPPase). The M. suis sPPase consists of 164 amino acids with a molecular mass of 20 kDa. The highest identity of 63.7% was found to the M. penetrans sPPase. The typical 13 active site residues as well as the cation binding signature could be also identified in the M. suis sPPase. The activity of the M. suis enzyme was strongly dependent on Mg2+ and significantly lower in the presence of Mn2+ and Zn2+. Addition of Ca2+ and EDTA inhibited the M. suis sPPase activity. These characteristics confirmed the affiliation of the M. suis PPase to family I soluble PPases. The highest activity was determined at pH 9.0. In M. suis the sPPase builds tetramers of 80 kDa which were detected by convalescent sera from experimentally M. suis infected pigs. CONCLUSION: The identification and characterization of the sPPase of M. suis is an additional step towards the clarification of the metabolism of hemotrophic mycoplasmas and, thus, important for the establishment of an in vitro cultivation system. As an antigenic and conserved protein the M. suis sPPase could in future be further analyzed as a diagnostic antigen

Ventricular pre-excitation in cats: 17 cases

Objectives: Atrioventricular accessory pathways are abnormal electrical connections between the atria and ventricles that predispose to ventricular pre-excitation (VPE) and tachycardias. Animals: Seventeen cats with VPE and 15 healthy matched-control cats. Material and methods: Multicenter case-control retrospective study. Clinical records were searched for cats with VPE, defined as preserved atrioventricular synchrony, reduced PQ interval, and increased QRS complex duration with a delta wave. Clinical, electrocardiography, echocardiographic, and outcome data were collated. Results: Most cats with VPE were male (16/17 cats), non-pedigree cats (11/17 cats). Median age and mean body weight were 5.4 years (0.3-11.9 years) and 4.6 ± 0.8 kg, respectively. Clinical signs at presentation included lethargy (10/17 cats), tachypnea (6/17 cats), and/or syncope (3/17 cats). In two cats, VPE was an incidental finding. Congestive heart failure was uncommon (3/17 cats). Nine (9/17) cats had tachyarrhythmias: 7/9 cats had narrow QRS complex tachycardia and 2/9 cats had wide QRS complex tachycardia. Four cats had ventricular arrhythmias. Cats with VPE had larger left (P < 0.001) and right (P < 0.001) atria and thicker interventricular septum (P = 0.019) and left ventricular free wall (P = 0.028) than controls. Three cats had hypertrophic cardiomyopathy. Treatment included different combinations of sotalol (5/17 cats), diltiazem (5/17 cats), atenolol (4/17 cats), furosemide (4/17 cats), and platelet inhibitors (4/17 cats). Five cats died, all from cardiac death (median survival time 1882 days [2-1882 days]). Conclusions: Cats with VPE had a relatively long survival, albeit showing larger atria and thicker left ventricular walls than healthy cats