Assessing mixed quantum-classical molecular dynamics methods for nonadiabatic dynamics of molecules on metal surfaces

Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional models for the scattering of diatomic molecules at metal surfaces based on recently published electronic structure data. We apply several MQC methods to investigate their ability to capture how nonadiabatic effects influence molecule-metal energy transfer during the scattering process. Specifically, we compare molecular dynamics with electronic friction, Ehrenfest dynamics, Independent Electron Surface Hopping, and the Broadened Classical Master Equation approach. In the case of Independent Electron Surface Hopping, we implement a simple decoherence correction approach and assess its impact on vibrationally-inelastic scattering. Our results show that simple, low-dimensional models can be used to qualitatively capture experimentally observed vibrational energy transfer and provide insight into the relative performance of different MQC schemes. We observe that all approaches predict similar kinetic energy dependence, but return different vibrational energy distributions. Finally, by varying the molecule-metal coupling, we can assess the coupling regime in which some MQC methods become unsuitable.Comment: 15 pages, 13 figure

Cryoprotection of Platelets by Grafted Polymers

Unlike red blood cells (RBC) which are stored at 4°C, platelets are stored at 22–24°C (room temperature) due to biophysical and biochemical changes induced by cold temperatures aggregately known as the ‘cold storage lesion’ (CSL). However, 22°C storage greatly increases the risk of microbial growth, thus limiting the safe storage of platelets to only 5–7 days (versus 42 days for RBC). Consequent to the short shelf life of platelets, blood services face chronic shortages of these life-saving cells. To overcome both the risk of microbial contamination and the constrained supplies of platelets, renewed research into attenuating the CSL and/or determining where cold stored platelets are clinically suitable are ongoing. In this chapter, we show that the covalent grafting of methoxypolyethylene glycol (mPEG), a biocompatible polymer, to the membrane of platelets attenuates the CSL. Moreover, the grafted mPEG serves as a potent cryoprotectant allowing platelets to be stored at 4°C, or frozen at −20°C, while retaining normal platelet counts and biologic function. The successful development of platelet PEGylation may provide a means by which the cold storage of platelets can be achieved with a minimal loss of platelet quality while improving both platelet microbial safety and inventory

Anthropology with Business: Plural Programs and Future Financial Worlds

How can we imagine and perform an anthropological practice with business, that is, not from a distanced perspective but through a mutual infolding and engagement? How might such an arrangement then be exemplary for novel economic experiments of the kind anthropologists often describe? Reflecting on several years' of collaborations with each other, the authors recount their relationship as an experiment in novel engagements with economic things (money, corporations, universities, accounting principles, computers, etc.) in an industrial and university site. The paper puts forward a theoretical argument about exaptive and nonadaptive plurality that opens new pathways for alternative and sometimes quite conventional values. The context is a specific set of projects around money and payment. The intellectual background is the anthropology of finance and alternative economies

H-Diplo Roundtable XX-20 on Matthew J. Ambrose. The Control Agenda: A History of the Strategic Arms Limitation Talks

A set of reviews of Matthew J. Ambrose\u27s The Control Agenda: A History of the Strategic Arms Limitation Talks, with a response from the author

Importance of equivariant features in machine-learning interatomic potentials for reactive chemistry at metal surfaces

Reactive chemistry of molecular hydrogen at surfaces, notably dissociative sticking and hydrogen evolution, play a crucial role in energy storage, fuel cells, and chemical synthesis. Copper is a particularly interesting metal for studying these processes due to its widespread use as both a catalyst in industry and a model catalyst in fundamental research. Theoretical studies can help to decipher underlying mechanisms and reaction design, but studying these systems computationally is challenging due to the complex electronic structure of metal surfaces and the high sensitivity towards reaction barriers. In addition, ab initio molecular dynamics, based on density functional theory, is too computationally demanding to explicitly simulate reactive sticking or desorption probabilities. A promising solution to such problems can be provided through high-dimensional machine learning-based interatomic potentials (MLIPs). Despite the remarkable accuracy and fidelity of MLIPs, particularly in molecular and bulk inorganic materials simulations, their application to different facets of hybrid systems and the selection of appropriate representations remain largely unexplored. This paper addresses these issues and investigates how feature equivariance in MLIPs impacts adaptive sampling workflows and data efficiency. Specifically, we develop high-dimensional MLIPs to investigate reactive hydrogen scattering on copper surfaces and compare the performance of various MLIPs that use equivariant features for atomic representation (PaiNN) with those that use invariant representations (SchNet). Our findings demonstrate that using equivariant features can greatly enhance the accuracy and reliability of MLIPs for gas surface dynamics and that this approach should become the standard in this field

Survival after bidirectional cavopulmonary anastomosis: Analysis of preoperative risk factors

ObjectivePrognostic factors for survival after bidirectional cavopulmonary anastomosis for functionally single ventricle are not well defined. We analyzed preoperative hemodynamic and echocardiographic data to determine risk factors for death or transplantation at least 1 year after bidirectional cavopulmonary anastomosis.MethodsData for all patients who underwent bidirectional cavopulmonary anastomosis before 5 years of age at our institution from September 1995 through June 2005 were analyzed. Available preoperative echocardiograms and catheterizations were reviewed. Survivors were compared with those who died or underwent transplantation. Bivariable associations between demographic and clinical risk factors and survival status (alive without transplantation vs dead or transplanted) were assessed with Wilcoxon rank sum test and χ2 or Fisher exact tests. Survival functions were constructed with Kaplan–Meier estimates, and event times compared between subgroups with log–rank tests. Cox proportional hazard modeling was used for multivariable modeling of risk of death or transplantation.ResultsOne hundred sixty-seven patients underwent bidirectional cavopulmonary anastomosis with hemi-Fontan (n = 62) or bidirectional Glenn (n = 105) operations. Three patients died before discharge, 11 died later, and 1 has undergone transplantation. Freedom from death or transplantation after bidirectional cavopulmonary anastomosis was 96% at 1 year and 89% at 5 years. Multivariable analysis of preoperative variables showed atrioventricular valve regurgitation to be an independent risk factor for death or transplantation (hazard ratio 2.8, 95% confidence interval 1.1–7.1, P = .02).ConclusionAlthough survival after bidirectional cavopulmonary anastomosis is high, preoperative atrioventricular valve regurgitation is an important risk factor for death or transplantation

Length of polynomials over finite groups

This document is the Accepted Manuscript version of the following article: Gábor Horváth, and Chrystopher L. Nehaniv, ‘Length of polynomials over finite groups’, Journal of Computer and System Sicences, Vol. 81(8): 1614-1622, December 2015. The final, published version is available online at doi: https://doi.org/10.1016/j.jcss.2015.05.002.We study the length of polynomials over finite simple non-Abelian groups needed to realize Boolean functions. We apply the results for bounding the length of 5-permutation branching programs recognizing a Boolean set. Moreover, for Boolean and general functions on these groups, we present upper bounds on the length of shortest polynomials computing an arbitrary n-ary Boolean or general function, or a function given by another polynomial.Peer reviewe