Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Probabilistic models”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,765 records · Page 98

Characterizing the uncertainty in holddown post load measurements

In order to understand unexpectedly erratic load measurements in the launch-pad supports for the space shuttle, the sensitivities of the load cells in the supports were analyzed using simple probabilistic techniques. NASA engineers use the loads in the shuttle's supports to calculate critical stresses in the shuttle vehicle just before lift-off. The support loads are measured with 'load cells' which are actually structural components of the mobile launch platform which have been instrumented with strain gauges. Although these load cells adequately measure vertical loads, the horizontal load measurements have been erratic. The load measurements were simulated in this study using Monte Carlo simulation procedures. The simulation studies showed that the support loads are sensitive to small deviations in strain and calibration. In their current configuration, the load cells will not measure loads with sufficient accuracy to reliably calculate stresses in the shuttle vehicle. A simplified model of the holddown post (HDP) load measurement system was used to study the effect on load measurement accuracy for several factors, including load point deviations, gauge heights, and HDP geometry.

Richardson, J. A.↗

Probabilistic Study Conducted on Sensor-Based Engine Life Calculation

Turbine engine life management is a very complicated process to ensure the safe operation of an engine subjected to complex usage. The challenge of life management is to find a reasonable compromise between the safe operation and the maximum usage of critical parts to reduce maintenance costs. The commonly used "cycle count" approach does not take the engine operation conditions into account, and it oversimplifies the calculation of the life usage. Because of the shortcomings, many engine components are regularly pulled for maintenance before their usable life is over. And, if an engine has been running regularly under more severe conditions, components might not be taken out of service before they exceed their designed risk of failure. The NASA Glenn Research Center and its industrial and academic partners have been using measurable parameters to improve engine life estimation. This study was based on the Monte Carlo simulation of 5000 typical flights under various operating conditions. First a closed-loop engine model was developed to simulate the engine operation across the mission profile and a thermomechanical fatigue (TMF) damage model was used to calculate the actual damage during takeoff, where the maximum TMF accumulates. Next, a Weibull distribution was used to estimate the implied probability of failure for a given accumulated cycle count. Monte Carlo simulations were then employed to find the profiles of the TMF damage under different operating assumptions including parameter uncertainties. Finally, probabilities of failure for different operating conditions were analyzed to demonstrate the importance of a sensor-based damage calculation in order to better manage the risk of failure and on-wing life.

Guo, Ten-Huei↗

Cellular, molecular, and therapeutic characterization of pilocarpine-induced temporal lobe epilepsy

Animal models have expanded our understanding of temporal lobe epilepsy (TLE). However, translating these to cell-specific druggable hypotheses is not explored. Herein, we conducted an integrative insilico-analysis of an available transcriptomics dataset obtained from animals with pilocarpine-induced-TLE. A set of 119 genes with subtle-to-moderate impact predicted most forms of epilepsy with ~ 97% accuracy and characteristically mapped to upregulated homeostatic and downregulated synaptic pathways. The deconvolution of cellular proportions revealed opposing changes in diverse cell types. The proportion of nonneuronal cells increased whereas that of interneurons, except for those expressing vasoactive intestinal peptide (Vip), decreased, and pyramidal neurons of the cornu-ammonis (CA) subfields showed the highest variation in proportion. A probabilistic Bayesian-network demonstrated an aberrant and oscillating physiological interaction between nonneuronal cells involved in the blood–brain-barrier and Vip interneurons in driving seizures, and their role was evaluated insilico using transcriptomic changes induced by valproic-acid, which showed opposing effects in the two cell-types. Additionally, we revealed novel epileptic and antiepileptic mechanisms and predicted drugs using causal inference, outperforming the present drug repurposing approaches. These well-powered findings not only expand the understanding of TLE and seizure oscillation, but also provide predictive biomarkers of epilepsy, cellular and causal micro-circuitry changes associated with it, and a drug-discovery method focusing on these events.

60 APPLIED LIFE SCIENCES↗

A Compilation of MATLAB Scripts and Functions for MACGMC Analyses

The primary aim of the current effort is to provide scripts that automate many of the repetitive pre- and post-processing tasks associated with composite materials analyses using the Micromechanics Analysis Code with the Generalized Method of Cells. This document consists of a compilation of hundreds of scripts that were developed in MATLAB (The Mathworks, Inc., Natick, MA) programming language and consolidated into 16 MATLAB functions. (MACGMC). MACGMC is a composite material and laminate analysis software code developed at NASA Glenn Research Center. The software package has been built around the generalized method of cells (GMC) family of micromechanics theories. The computer code is developed with a user-friendly framework, along with a library of local inelastic, damage, and failure models. Further, application of simulated thermo-mechanical loading, generation of output results, and selection of architectures to represent the composite material have been automated to increase the user friendliness, as well as to make it more robust in terms of input preparation and code execution. Finally, classical lamination theory has been implemented within the software, wherein GMC is used to model the composite material response of each ply. Thus, the full range of GMC composite material capabilities is available for analysis of arbitrary laminate configurations as well. The pre-processing tasks include generation of a multitude of different repeating unit cells (RUCs) for CMCs and PMCs, visualization of RUCs from MACGMC input and output files and generation of the RUC section of a MACGMC input file. The post-processing tasks include visualization of the predicted composite response, such as local stress and strain contours, damage initiation and progression, stress-strain behavior, and fatigue response. In addition to the above, several miscellaneous scripts have been developed that can be used to perform repeated Monte-Carlo simulations to enable probabilistic simulations with minimal manual intervention. This document is formatted to provide MATLAB source files and descriptions of how to utilize them. It is assumed that the user has a basic understanding of how MATLAB scripts work and some MATLAB programming experience.

Materials Engineering↗

GSplit: Scaling Graph Neural Network Training on Large Graphs via Split-Parallelism

Graph neural networks (GNNs), an emerging class of machine learning models for graphs, have gained popularity for their superior performance in various graph analytical tasks. Mini-batch training is commonly used to train GNNs on large graphs, and data parallelism is the standard approach to scale mini-batch training across multiple GPUs. Data parallel approaches contain redundant work as subgraphs sampled by different GPUs contain significant overlap. To address this issue, we introduce a hybrid parallel mini-batch training paradigm called Split parallelism. Split parallelism avoids redundant work by splitting the sampling, loading, and training of each mini-batch across multiple GPUs. Split parallelism, however, introduces communication overheads that can be more than the savings from removing redundant work. We further present a lightweight partitioning algorithm that probabilistically minimizes these overheads. We implement spllit parllelism in GSplit and show that it outperforms state-of-the-art mini-batch training systems like DGL, Quiver, and P3.

Lim, Seung-Hwan [ORNL] (ORCID:0000000194616866)↗

Control of Risks Through the Use of Procedures: A Method for Evaluating the Change in Risk

This paper considers how procedures can be used to control risks faced by an organization and proposes a means of recognizing if a particular procedure reduces risk or contributes to the organization's exposure. The proposed method was developed out of the review of work documents and the governing procedures performed in the wake of the Columbia accident by NASA and the Space Shuttle prime contractor, United Space Alliance, LLC. A technique was needed to understand the rules, or procedural controls, in place at the time in the context of how important the role of each rule was. The proposed method assesses procedural risks, the residual risk associated with a hazard after a procedure's influence is accounted for, by considering each clause of a procedure as a unique procedural control that may be beneficial or harmful. For procedural risks with consequences severe enough to threaten the survival of the organization, the method measures the characteristics of each risk on a scale that is an alternative to the traditional consequence/likelihood couple. The dual benefits of the substitute scales are that they eliminate both the need to quantify a relationship between different consequence types and the need for the extensive history a probabilistic risk assessment would require. Control Value is used as an analog for the consequence, where the value of a rule is based on how well the control reduces the severity of the consequence when operating successfully. This value is composed of two parts: the inevitability of the consequence in the absence of the control, and the opportunity to intervene before the consequence is realized. High value controls will be ones where there is minimal need for intervention but maximum opportunity to actively prevent the outcome. Failure Likelihood is used as the substitute for the conventional likelihood of the outcome. For procedural controls, a failure is considered to be any non-malicious violation of the rule, whether intended or not. The model used for describing the Failure Likelihood considers how well a task was established by evaluating that task on five components. The components selected to define a well established task are: that it be defined, assigned to someone capable, that they be trained appropriately, that the actions be organized to enable proper completion and that some form of independent monitoring be performed. Validation of the method was based on the information provided by a group of experts in Space Shuttle ground processing when they were presented with 5 scenarios that identified a clause from a procedure. For each scenario, they recorded their perception of how important the associated rule was and how likely it was to fail. They then rated the components of Control Value and Failure Likelihood for all the scenarios. The order in which each reviewer ranked the scenarios Control Value and Failure Likelihood was compared to the order in which they ranked the scenarios for each of the associated components; inevitability and opportunity for Control Value and definition, assignment, training, organization and monitoring for Failure Likelihood. This order comparison showed how the components contributed to a relative relationship to the substitute risk element. With the relationship established for Space Shuttle ground processing, this method can be used to gauge if the introduction or removal of a particular rule will increase or decrease the .risk associated with the hazard it is intended to control.

Praino, Gregory T.↗

Exploratory analysis of machine learning techniques in the Nevada geothermal play fairway analysis

Play fairway analysis (PFA) is commonly used to generate geothermal potential maps and guide exploration studies, with a particular focus on locating and characterizing blind geothermal systems. This study evaluates the application of machine learning techniques to PFA in the Great Basin region of Nevada. Following the evaluation of various techniques, we identified two approaches to PFA that produced promising results, 1) supervised Bayesian probabilistic neural networks to generate geothermal potential maps with confidence intervals, and 2) unsupervised principal component analysis paired with k-means clustering to generate both cluster maps to help identify spatial patterns, as well as new combined feature inputs. We applied these techniques to perform a comparative analysis between two principal sets of geological and geophysical features related to permeability and heat and a set of positive (known geothermal resources) and negative training sites (known drill sites with unsuitable geothermal conditions). We found that these methods constrain previously unrecognized feature controls on geothermal favorability, many of which are spatially organized within the extent of cluster groups and the major structural-hydrologic domains of the study area. Furthermore, we utilized exploratory unsupervised modeling to highlight spatial relationships between input data and predictive output results of our supervised modeling. As a result, we demonstrate how our models compare to the previous Nevada PFA and how the rapid insights these machine learning techniques offer may support future assessments of both known and undiscovered blind geothermal systems in the Great Basin region of Nevada and beyond.

15 GEOTHERMAL ENERGY↗

A Probabilistic Method of Assessing Carbon Accumulation Rate at Imnavait Creek Peatland, Arctic Long Term Ecological Research Station, Alaska

Arctic peatlands are an important part of the global carbon cycle, accumulating atmospheric carbon as organic matter since the Late glacial. Current methods for understanding the changing efficiency of the peatland carbon sink rely on peatlands with an undisturbed stratigraphy. Here we present a method of estimating primary carbon accumulation rate from a site where permafrost processes have either vertically or horizontally translocated nearby carbon-rich sediment out of stratigraphic order. Briefly, our new algorithm estimates the probability of the age of deposition of a random increment of sediment in the core. The method assumes that if sediment age is measured at even depth increments, dates are more likely to occur during intervals of higher accumulation rate and vice versa. Multiplying estimated sedimentation rate by measured carbon density yields carbon accumulation rate. We perform this analysis at the Imnavait Creek Peatland, near the Arctic Long Term Ecological Research network site at Toolik Lake, Alaska. Using classical radiocarbon age modeling, we find unreasonably high rates of carbon accumulation at various Holocene intervals. With our new method, we find accumulation rate changes that are in improved agreement within the context of other sites throughout Alaska and the rest of the Circum-Arctic region.

carbon accumulation;Imnavait;peatlands;permafrost;↗

On the variability of the Bering Sea Cold Pool and implications for the biophysical environment

The Bering Sea experiences a seasonal sea ice cover, which is important to the biophysical environment found there. A pool of cold bottom water (<2°C) is formed on the shelf each winter as a result of cooling and vertical mixing due to brine rejection during the predominately local sea ice growth. The extent and distribution of this Cold Pool (CP) is largely controlled by the winter extent of sea ice in the Bering Sea, which can vary considerably and recently has been much lower than average. The cold bottom water of the CP is important for food security because it delineates the boundary between arctic and subarctic demersal fish species. A northward retreat of the CP will likely be associated with migration of subarctic species toward the Chukchi Sea. We use the fully-coupled Regional Arctic System Model (RASM) to examine variability of the extent and distribution of the CP and its relation to change in the sea ice cover in the Bering Sea during the period 1980–2018. RASM results confirm the direct correlation between the extent of sea ice and the CP and show a smaller CP as a consequence of realistically simulated recent declines of the sea ice cover in the Bering Sea. In fact, the area of the CP was found to be only 31% of the long-term mean in July of 2018. In addition, we also find that a low ice year is followed by a later diatom bloom, while a heavy ice year is followed by an early diatom bloom. Finally, the RASM probabilistic intra-annual forecast capability is reviewed, based on 31-member ensembles for 2019–2021, for its potential use for prediction of the winter sea ice cover and the subsequent summer CP area in the Bering Sea.

54 ENVIRONMENTAL SCIENCES↗

Estimating IDP Origins Using ACLED Political Violence Events: Validation with Lebanon IDP Flow Data

A key input in modeling population distribution and flows following conflict events is the inclusion of Internally Displaced Person (IDP) flows between administrative units within a country. These flows are critical for capturing population movement and redistribution driven by current events, particularly conflict. In some cases, IDP destination data are available while origin data is incomplete or unavailable. This creates a gap in understanding where displacement is occurring, limiting the ability to model population redistribution accurately. Without origin data, it is not possible to reallocate population flows or accurately represent where displacement is occurring within the country. This report evaluates whether Armed Conflict Location Event Data (ACLED) political violence event data can be used to estimate IDP origin distributions when direct origin data are unavailable. The approach is validated using historical IDP flow data from Lebanon, where both origins and destinations are observed. Results show that ACLED event distributions strongly correspond to observed IDP-origin patterns, particularly when using cumulative 60-day event windows. The method is most reliable for identifying major origin districts and approximating proportional origin shares. However, it is not intended to reconstruct exact individual displacement flows, but rather to provide a probabilistic spatial allocation of displacement origins.

99 GENERAL AND MISCELLANEOUS↗

Enabling Cybersecurity, Situational Awareness and Resilience in Distribution Grids with High Penetration of Photovoltaics (CARE-PV) (Final Report)

Since legacy distribution systems have very limited visibility beyond the substation, high penetration of PV at the grid edge presents some unique operational challenges. One approach to address these challenges is to use information from advanced metering infrastructure (AMI) and µPMUs. However, exploiting this information is impacted by a number of factors, including multi-timescale measurements, volume of data generated, communication network impairments (e.g., information loss and latency) and susceptibility to cyber-attacks. Therefore, one of the critical tasks involved in the management of a distribution grid is to develop complete situational awareness by integrating cyber-security mechanisms with state estimation strategies and leveraging this situational awareness to assure energy services at strategic locations while exploiting AMI/PV inverter/ µPMU data. This CARE-PV project addresses the fundamental challenges in situational awareness and resilience to cyber and physical vectors by exploiting the synergy between innovative modeling, estimation, data analytics, testing and validation using smart PV inverters designed at K-State and facilities at NREL. Specifically, the project involved the development, testing and validation of the following novel enabling technologies: (Thrust 1) Resilience to cyber vectors that impact data integrity was addressed via a two-level defense strategy that combines cyber intrusion detection using self-learning, cooperative smart PV inverters, and a novel moving target defense framework to combat data integrity attacks. (Thrust 2) Resilience to cyber-physical vectors that impact situational awareness by limiting data availability was addressed via novel centralized and decentralized, sparsity-based static and dynamic state estimation approaches that enhance observability even when the underlying system is unobservable. (Thrust 3) Leveraging a unique probabilistic sensitivity analysis approach accompanied by one-of-a-kind dominant influencer set computation, the vulnerability of critical infrastructure at strategic locations was evaluated so that proactive PV-based control strategies can be used to support operations under normal/outage scenarios. These CARE-PV project innovations were demonstrated on both small-scale IEEE and larger utility-scale testbeds (Thrust 4). Feedback from Industry Advisory Board members was used to formulate a commercialization pathway for a subset of CARE-PV technologies. These CARE-PV technologies will ultimately lead to reliable and secure, large-scale integration of renewable energy and mitigate the risk of energy disruption resulting from cyber incidents and other emerging threats within the energy environment.

14 SOLAR ENERGY↗

An Integrated Reliability and Physics-Based Risk Modeling Approach for Assessing Human Spaceflight Systems

This paper presents an integrated reliability and physics-based risk modeling approach for assessing human spaceflight systems. The approach is demonstrated using an example, end-to-end risk assessment of a generic-crewed space transportation system during a reference mission to the International Space Station. The behavior of the system is modeled using analysis techniques from multiple disciplines in order to properly capture the dynamic time- and state- dependent consequences of failures encountered in different mission phases. We discuss how to combine traditional reliability analyses with Monte Carlo simulation methods and physics-based engineering models to produce loss-of- mission and loss-of-crew risk estimates supporting risk-based decision-making and requirement verification. This approach facilitates risk-informed design by providing more realistic representation of system failures and interactions; identifying key risk-driving sensitivities, dependencies, and assumptions; and tracking multiple figures of merit within a single, responsive assessment framework that can readily incorporate evolving design information throughout system development.

Risk assessment↗

Stochastic Control Synthesis of Systems with Structured Uncertainty

This paper presents a study on the design of robust controllers by using random variables to model structured uncertainty for both SISO and MIMO feedback systems. Once the parameter uncertainty is prescribed with probability density functions, its effects are propagated through the analysis leading to stochastic metrics for the system's output. Control designs that aim for satisfactory performances while guaranteeing robust closed loop stability are attained by solving constrained non-linear optimization problems in the frequency domain. This approach permits not only to quantify the probability of having unstable and unfavorable responses for a particular control design but also to search for controls while favoring the values of the parameters with higher chance of occurrence. In this manner, robust optimality is achieved while the characteristic conservatism of conventional robust control methods is eliminated. Examples that admit closed form expressions for the probabilistic metrics of the output are used to elucidate the nature of the problem at hand and validate the proposed formulations.

Padula, Sharon L.↗

Blind Validation Study of Parametric Cost Estimation Tool SEER-H for NASA Space Missions

One of the primary parametric cost modeling tools used by NASA and the aerospace industry to estimate the development and production cost of future spacecraft hardware is SEER-H by Galorath. To date, no independent validation of this tool for cost estimation of space missions has been reported in the literature. In the present validation study, cost estimators used SEER-H to estimate the cost of twelve different past NASA science missions. The estimators were prevented from knowing the actual cost of the missions in an effort to minimize cognitive biases. The point estimates of SEER-H had an average error of 23%, median error of -0.3%, and a standard deviation of 43%. Nine of the twelve mission's actual costs fell within the 80% confidence interval of SEER's probabilistic estimates. Several factors independent of SEER that may have affected the accuracy of the results have been identified and are discussed; these include: uncertainty in the technical data used for the estimates, the methods used to estimate uncertainty in spacecraft component mass and numbers of prototypes, and the experience of the estimators.

SEER-H↗

SIMULATION CLONING FOR DIGITAL TWINS: A SCALABLE APPROACH

Digital Twin (DT) methods represent an important technology in which a simulated model of the operations of a physical system uses real-time sensor data to simulate, monitor, and consequently, improve its operations. One of the primary objectives of such a DT is to inform the physical system of measures to be taken in response to one or multiple intervening events that can change the state of the physical system. As such, a capability that is able to carry out multiple scenario assessments in real time in readiness for such events is a very effective tool in the use of simulations as DTs. However, continuous evaluation with highly probable event simulation scenarios are challenging due to the constraints of finite memory and a large exploration space. This paper reports a novel methodology for the continuous evaluation of $k$ probabilistic \textit{what-if} event scenarios under finite resource constraints and demonstrates its use as a digital-twin for a real-world application.

Yoginath, Srikanth↗

Comparative Analysis of Static and Dynamic Probabilistic Risk Assessment

Implementation of risk-informed design allows the design team to thoroughly explore the risks of a system while iterating the operations concept, design, and requirements until the system meets mission objects and is achievable within constraints. To arrive at a space system design that is likely to meet all constraints placed upon mass, cost, performance and risk, the system requirements must be understood and traded against each other as early as the conceptual design phase. Depending on the project phase and the goals of the risk analysis, various PRA methodologies could be used to produce quantitative risk estimates to enable such a process. In order to better understand the applicability, advantages, and limitations of various PRA methodologies, a comparative analysis of three bottom-up, component-based PRA approaches was performed. The three methods examined are a traditional static fault tree, a fault tree hybrid, and a dynamic Monte Carlo simulation. Each approach was used to assess a generic reaction control system (RCS) thruster pod and mission. The methods are assessed in terms of the process of modeling a system, the actionable information produced for the design team, and the overall fidelity of the quantitative risk evaluation generated. The paper also discusses the applicability of each methodology to the different phases of system development.

Probablistic↗

Complex Dynamics of Air Traffic Flow

Air traffic in the United States has continued to grow at a steady pace since 1980, except for a dip immediately after the tragic events of September 11, 2001. There are different growth scenarios associated both with the magnitude and the composition of the future air traffic. The Terminal Area Forecast (TAF), prepared every year by the FAA, projects the growth of traffic in the United States. Both Boeing and Airbus publish market outlooks for air travel annually. Although predicting the future growth of traffic is difficult, there are two significant trends: heavily congested major airports continue to see an increase in traffic, and the emergence of regional jets and other smaller aircraft with fewer passengers operating directly between non-major airports. The interaction between air traffic demand and the ability of the system to provide the necessary airport and airspace resources can be modeled as a network. The size of the resulting network varies depending on the choice of its nodes. It would be useful to understand the properties of this network to guide future design and development. Many questions, such as the growth of delay with increasing traffic demand and impact of the en route weather on future air traffic, require a systematic understanding of the properties of the air traffic network. There has been a major advance in the understanding of the behavior of networks with a large number of components. Several theories have been advanced about the evolution of large biological and engineering networks by authors in diversified disciplines like physics, mathematics, biology and computer science. Several networks exhibit a scale-free property in the sense that the probabilistic distribution of their nodes as a function of connections decreases slower than an exponential. These networks are characterized by the fact that a small number of components have a disproportionate influence on the performance of the network. Scale-free networks are tolerant to random failure of components, but are vulnerable to selective attack on components. This paper examines two network representations for the baseline air traffic system. A network defined with the 40 major airports as nodes and with standard flight routes as links has a characteristic scale: all nodes have 60 or more links and no node has more than 460 links. Another network is defined with baseline aircraft routing structure exhibits an exponentially truncated scale-free behavior. Its degree ranges from 2 connections to 2900 connections, and 225 nodes have more than 250 connections. Furthermore, those high-degree nodes are homogeneously distributed in the airspace. A consequence of this scale-free behavior is that the random loss of a single node has little impact, but the loss of multiple high-degree nodes (such as occurs during major storms in busy airspace) can adversely impact the system. Two future scenarios of air traffic growth are used to predict the growth of air traffic in the United States. It is shown that a three-times growth in the overall traffic may result in a ten-times impact on the density of traffic in certain parts of the United States.

Scale-free Networks↗

Acidities of MgO surface sites: implications for the formation mechanism of Mg(OH) 2

The hydroxylation of periclase (MgO) to brucite (Mg(OH) 2 ) is thought to be an important intermediate step when using MgO to capture CO 2 from the atmosphere. However, the mechanism of hydroxylation of MgO to form Mg(OH) 2 is poorly understood. In this work, we used atomic-scale density functional tight binding simulations coupled with the metadynamics rare event method to analyze the surface chemistry of MgO and the acid dissociation equilibrium constants (pK a ) of its surface sites. The method and parameters were validated by calculating the pK a for hydroxylation of the first shell water bound to aqueous Mg 2+ ion. The pK a value derived using a probabilistic method was 12.3, which is in fair agreement with the accepted value of 11.4, with the difference between them equal to a ∼5 kJ mol −1 error in the calculations. We then extended these pK a calculations to probe the hydroxylation reactions of the surface sites of the MgO(100)–water interface, arriving at pK a s of 5.4 to deprotonate terminal water molecules bound to the surface magnesium sites (η-OH 2 or 〉MgOH 2 ), and 13.9 to deprotonate hydroxylated bridging oxygen sites (μ 5 -oxo or 〉O). Hydroxide (OH − ) adsorption on the surface was also probed and found to be less thermodynamically favorable than deprotonation of the terminal water molecule. The plausibility of the computed pK a s was verified using an activity-based speciation model and compared to pH measurements of water equilibrated with MgO nanoparticles and single crystals. The model predicted a solution pH of 7.1 when surface sites buffered and the pH of 12.0 when MgO dissolution dominated. These are close to the experimental initial solution pHs of 7–7.5 and the long term pHs of ∼10.5. The similarity suggests that the calculated pK a values from the DFTB+/metadynamics simulations are plausible and that these methods can be a useful tool to probe reaction mechanisms involving covalent bonds.

Adapa, Sai Krishna Reddy [Oak Ridge National Labor↗