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Parameterization of Surface Fluxes in the VVR Fourth Order GCM

The Variable Vertical Resolution (VVR) option of the GLAS Fourth Order General Circulation Model (GCM) allows one to enhance the vertical resolution of the region of the atmosphere adjacent to the Earth's surface. This, in turn, makes it possible to compute turbulent surface fluxes of heat, momentum and moisture directly from the prognosticated properties of the lowest model layer by use of the Monin-Obukhov surface layer similarity theory. The similarity theory applies formally only to the constant flux surface layer which is but a few tens of meters deep. It is not practically feasible to work with a lowest GCM layer thin enough to satisfy these formal constraints. It is shown that at least under conditions of neutral stratification, the similarity theory can be extended beyond its formal limits. The theory still gives reasonable looking results, when the distance from the ground becomes as large as 150 m. It is not infeasible to run the VVR model with a lowest layer thickness on the order of 300 m (the center of the layer would then be 150 m above the Earth's surface), and so if one can prescribe similarity functions phi sub m (zeta) and phi sub h (zeta) to adequately describe the entire extended surface layer, the problem of surface flux parameterization is solved.

Helfand, H. M.

General purpose optimization software for engineering design

The author has developed several general purpose optimization programs over the past twenty years. The earlier programs were developed as research codes and served that purpose reasonably well. However, in taking the formal step from research to industrial application programs, several important lessons have been learned. Among these are the importance of clear documentation, immediate user support, and consistent maintenance. Most important has been the issue of providing software that gives a good, or at least acceptable, design at minimum computational cost. Here, the basic issues developing optimization software for industrial applications are outlined and issues of convergence rate, reliability, and relative minima are discussed. Considerable feedback has been received from users, and new software is being developed to respond to identified needs. The basic capabilities of this software are outlined. A major motivation for the development of commercial grade software is ease of use and flexibility, and these issues are discussed with reference to general multidisciplinary applications. It is concluded that design productivity can be significantly enhanced by the more widespread use of optimization as an everyday design tool.

Vanderplaats, G. N.

NASA Langley's Formal Methods Research in Support of the Next Generation Air Transportation System

This talk will provide a brief introduction to the formal methods developed at NASA Langley and the National Institute for Aerospace (NIA) for air traffic management applications. NASA Langley's formal methods research supports the Interagency Joint Planning and Development Office (JPDO) effort to define and develop the 2025 Next Generation Air Transportation System (NGATS). The JPDO was created by the passage of the Vision 100 Century of Aviation Reauthorization Act in Dec 2003. The NGATS vision calls for a major transformation of the nation s air transportation system that will enable growth to 3 times the traffic of the current system. The transformation will require an unprecedented level of safety-critical automation used in complex procedural operations based on 4-dimensional (4D) trajectories that enable dynamic reconfiguration of airspace scalable to geographic and temporal demand. The goal of our formal methods research is to provide verification methods that can be used to insure the safety of the NGATS system. Our work has focused on the safety assessment of concepts of operation and fundamental algorithms for conflict detection and resolution (CD&R) and self- spacing in the terminal area. Formal analysis of a concept of operations is a novel area of application of formal methods. Here one must establish that a system concept involving aircraft, pilots, and ground resources is safe. The formal analysis of algorithms is a more traditional endeavor. However, the formal analysis of ATM algorithms involves reasoning about the interaction of algorithmic logic and aircraft trajectories defined over an airspace. These trajectories are described using 2D and 3D vectors and are often constrained by trigonometric relations. Thus, in many cases it has been necessary to unload the full power of an advanced theorem prover. The verification challenge is to establish that the safety-critical algorithms produce valid solutions that are guaranteed to maintain separation under all possible scenarios. Current research has assumed perfect knowledge of the location of other aircraft in the vicinity so absolute guarantees are possible, but increasingly we are relaxing the assumptions to allow incomplete, inaccurate, and/or faulty information from communication sources.

Butler, Ricky W.

Orbital Debris Ontology, Terminology, and Knowledge Modeling

The looming threat orbital debris poses to assets in orbit demands solutions. As the orbital population grows, so does this hazard, but so does the sea of data. The problem is also an opportunity for interdisciplinary innovation and cooperation. This paper focuses on the data and information management aspect of developing solutions for a sustainable and safe orbital space environment. The corresponding author’s in-progress work to develop an orbital debris domain ontology is summarized in order to discuss knowledge modeling for this domain. Methodological approaches of this effort can also contribute to standards efforts and address terminological and policy questions. Leveraging the growing volumes of orbital debris and space situational awareness (SSA) data will create a more complete picture of the orbital space environment. Part of the solution will be: consistent and correct data interpretation, sharing orbital debris and SSA data in one form or another, terminology development & harmonization, and knowledge or domain modeling. To facilitate this, [Rovetto, 2015/16] discussed ontology development for the orbital debris domain. This paper lists concepts from that paper, and subsequently developed concepts [2-9]. Ontology engineering is an interdisciplinary field related to knowledge representation and reasoning in artificial intelligence, semantic technologies and the so-called semantic web. An ontology is effectively a computable and semantically rich terminology that presents a knowledge or domain model for a topic area. Expressions of knowledge or assertions are stored using formally defined term. This knowledge base is reasoned over to yield answers to queries, among other things. Ontologies have been developed in knowledge-based projects across various disciplines, and used for such things as search engines, chatbots, enterprise knowledge graphs, etc. Ontologies support: interoperability, automated reasoning, data sharing and integration, data search and retrieval, and communicating the meaning of data. The Orbital Debris Ontology (ODO), and related ontologies [Rovetto & Kelso 2016] [Rovetto 2016, 2017], were proposed to help achieve this. ODO, for instance, is intended as a domain ontology that can be used across federated databases, offering an explicitly specified set of concepts describing the orbital debris domain. Its meaning-rich taxonomy will provide a sharable semantics for orbital debris data to, in part, consistently communicate the meaning of data to both humans and machines, and tag data elements in space object catalogs to help afford inference tasks, decision support, knowledge discovery, and information integration. ODO and the SSA ontology (SSAO) is part of the overall Orbital Space Domain Ontology concept, which is conceived as a broader domain reference ontology. It aims to provide a knowledge representation structure of the orbital space environment, a common semantic model, and develop a sharable terminology. Collectively this will provide common meaning for datasets, a high-level taxonomy or classification for orbital space objects, and thus means to characterize space objects. Ongoing efforts have included using visualizations, R, JSON-LD, and contemporary semantic technologies. Potential applications and interdisciplinary partnerships include web-based platforms, web apps, visualizations, and academia projects. Community input and participation may yield a more widely understood domain model as well as facilitate terminological standards. For example, the proposed conceptual, terminological and ontological analysis may contribute to such efforts as the Space Debris Mitigation Requirements in the International Standards Organization by developing more precise, consistent and coherent terms and definitions. Projects that seek to develop in-house ontologies can use ODO and related ontologies as domain reference ontologies. This paper was developed independent of author affiliations. Readers are encouraged to contact corresponding author(1) with general interest and potential opportunities to support or realize the described project.

Robert J. Rovetto

Autonomous Ocean World Exploration: Advancement of a Virtual Testbed

The search for life (extinct or extant) and potentially habitable bodies in our solar system and beyond is one of the 12 priority science questions outlined in the National Acadamies’ 2022 decadal survey [5]. Extraterrestrial destinations containing liquid water present an opportunity to search for life as we know it, and in recent years an increasing number of such locations have been discovered within our solar system. Several Jovian moons—Europa, Ganymede, and Callisto [10]—and the Saturnian moons Enceladus [8] and Titan [9] are known or suspected to harbor massive subsurface oceans. Of these "ocean worlds", Europa is the focus of at least one planned NASA orbiter mission, Europa Clipper [4], and an early lander mission concept, the Europa Lander [2, 3]. Whereas most robotic missions to the Moon and Mars (e.g. orbiters, rovers, landers) to date have had ground controllers on Earth tightly involved in mission operations, missions to more distant worlds will require a high degree of onboard autonomy due to long communication lags and blackouts, harsh environments (radiation, cold), and more limited battery and hardware life. The past decade has seen great advances in both AI technologies and computing scalability and performance that offer promising solutions for spacecraft autonomy and motivate the software system and research programs described in this paper. The Ocean Worlds Autonomy Testbed for Exploration, Research, and Simulation (OceanWATERS) [1], which has been in development at the NASA Ames Research Center since 2018, is a virtual environment for testing lander autonomy solutions. It is built on the Robot Operating System (ROS), runs on consumer-grade Linux workstations, and was released as open source in 2020. OceanWATERS provides a physical and visual simulation of a prototypical lander in a Europa-like environment (Figure 1). The lander was modeled after requirements and specifications made in JPL’s Europa Lander Study of 2016 [3]. Simulated lander systems include stereo cameras and spotlights mounted on an antenna mast that pans and tilts, a 6 degrees of freedom (DoF) robotic arm with a force-torque sensor and two interchangeable end effectors, and a battery pack power system. The environment consists of multiple terrain models including a highly detailed model sourced from the FROST dataset [11], simulation of surrounding planetary bodies based on an ephemeris model, and lighting from the sun with associated surface illumination, reflectance, and shadows. Operations supported by OceanWATERS include panoramic and directed imaging of the environment and lander workspace, Cartesian and joint-level arm commanding, grinding of the terrain surface (e.g. digging a trench), and scooping of ground material (Figure 2) which can be discarded or collected as science samples in a receptacle that can be emptied (science operations themselves are not simulated). These operations are realized as ROS Actions and are complimented by a wide selection of telemetry that is continually produced by each lander subsystem. The power system model is driven by the open-source Generic Software Architecture for Prognostics (GSAP) [11] that predicts the battery’s remaining useful life and other characteristics. As a testbed for high-level autonomy, OceanWATERS provides an execution framework based on PLEXIL [12], an open-source plan specification language and execution engine developed largely at Ames. NASA's initial development of OceanWATERS, as well the Ocean Worlds Lander Autonomy Testbed (OWLAT) [6], a complimentary physical testbed developed at JPL, was the first step in a plan for realizing candidate onboard autonomy solutions for such planetary landers. In 2020 NASA solicited applications for its Autonomous Robotics Research for Ocean Worlds (ARROW) program, and in 2021 the similar Concepts for Ocean worlds Life Detection Technology (COLDTech) program. Collectively six research teams, based in universities and companies across the United States, were awarded grants to develop and demonstrate autonomy solutions on OceanWATERS and OWLAT. These 1–2-year projects have now finished or are nearing completion, and a wide variety of autonomy challenges in ocean world surface missions were addressed. Prototyped and demonstrated solutions have included autonomous discovery, response and adaptation to system faults and unexpected environmental events, world model synthesis through perception, plan synthesis using learned models, methods to optimize sample target selection and prioritize science data transmission, extension of PLEXIL for stochastic decision-making, and an integration of a model of JPL’s mission-ready COLDArm [7]. Technologies used in these projects include many forms of machine learning, causal reasoning, automated planning, Markov decision processes, formal methods, and other advanced techniques. A more detailed summary of the ARROW and COLDTech projects is given herein. OceanWATERS has had significant enhancements since its open-source release in 2020. Many of its new features were driven or shaped by feedback from the ARROW and COLDTech teams and requirements of their projects. In support of enabling autonomous adaptation to spacecraft faults (a specific capability solicited by both programs), a fault injection and detection framework was developed that supports a wide and growing range of fault types such as locked joints, image loss, and battery failures. The power system model was completed and integrated into the simulator, starting as a single-cell battery model and later upgraded to a multi-cell model with associated faults such as cell disconnection. Arm/terrain interaction was improved by adding a force-torque sensor and associated faults, and an analytic dig force model based on the Balovnev bucket force equations. Environment fidelity was increased by modeling terrain deformation resulting from digging and scooping; visual improvements were made in textures, lighting, and shadows. To facilitate interoperation with OWLAT, a unified command and telemetry interface between the testbeds was developed at the ROS level, along with a PLEXIL interface. The number of lander operations was greatly expanded (e.g. with Cartesian-based arm and antenna movement), and a framework was designed for users to build their own lander actions. A GUI for PLEXIL plan selection was created (Figure 3), and an expansive set of plans were added, such as those that illustrate patterns for fault handling. This paper provides a self-contained high-level description of OceanWATERS, focusing on more detailed coverage of the aforementioned enhancements. It provides a high-level summary of the projects undertaken by participants in the ARROW and COLDTech programs and how these efforts have helped shape OceanWATERS. Finally, potential future work and directions for the testbed are listed, as likely informed by the recent planetary science decadal survey [5].

K Michael Dalal

A secondary tracer approach to the derivation of galactic cosmic-ray source isotopic abundances

A formalism has been developed for deriving cosmic-ray source isotopic abundances from observed local abundances using a purely secondary nuclide as a tracer of spallation production during propagation. Although the formalism is based on the leaky-box model of cosmic-ray propagation, it is shown that source abundances derived by the tracer technique are reasonably independent of detailed propagation models. The tracer formalism also permits a quantitative evaluation of the effects of observational uncertainties on deduced source abundances. It is shown that statistical errors in the observed abundances and uncertainties in the spallation cross sections are at present the dominant sources of uncertainty. The latter error can be reduced with increased detector size or exposure time, while the former can be minimized by measurements of the relative production cross sections. As a specific example, the tracer technique is applied to the isotopes of sulfur and calcium, and the level of uncertainties which must be achieved to distinguish evolutionary differences between solar-system material and cosmic ray-source material are established.

Stone, E. C.

AR4IR (Automated Reasoning for Incident Response) [SWR-24-103]

A basic formal methods tool with the ability to aid and/or automate a utilities’ incidence response and instills confidence that the proposed action satisfies the system’s physical constraints, the organization’s cyber policies, and will not cause violations of technical standards.

Etigowni, Sriharsha [National Renewable Energy Lab

DRS: Derivational Reasoning System

The high reliability requirements for airborne systems requires fault-tolerant architectures to address failures in the presence of physical faults, and the elimination of design flaws during the specification and validation phase of the design cycle. Although much progress has been made in developing methods to address physical faults, design flaws remain a serious problem. Formal methods provides a mathematical basis for removing design flaws from digital systems. DRS (Derivational Reasoning System) is a formal design tool based on advanced research in mathematical modeling and formal synthesis. The system implements a basic design algebra for synthesizing digital circuit descriptions from high level functional specifications. DRS incorporates an executable specification language, a set of correctness preserving transformations, verification interface, and a logic synthesis interface, making it a powerful tool for realizing hardware from abstract specifications. DRS integrates recent advances in transformational reasoning, automated theorem proving and high-level CAD synthesis systems in order to provide enhanced reliability in designs with reduced time and cost.

Bose, Bhaskar

The Transition from Spacecraft Development Ot Flight Operation: Human Factor Considerations

In the field of aeronautics and astronautics, a paradigm shift has been witnessed by those in academia, research and development, and private industry. Long development life cycles and the budgets to support such programs and projects has given way to aggressive task schedules and leaner resources to draw from all the while challenging assigned individuals to create and produce improved products of processes. however, this "faster, better, cheaper" concept cannot merely be applied to the design, development, and test of complex systems such as earth-orbiting of interplanetary robotic spacecraft. Full advantage is not possible without due consideration and application to mission operations planning and flight operations, Equally as important as the flight system, the mission operations system consisting of qualified personnel, ground hardware and software tools, and verified and validated operational processes, should also be regarded as a complex system requiring personnel to draw upon formal education, training, related experiences, and heuristic reasoning in engineering an effective and efficient system. Unquestionably, qualified personnel are the most important elements of a mission operations system. This paper examines the experiences of the Deep Space I Project, the first in a series of new technology in-flight validation missions sponsored by the United States National Aeronautics and Space Administration (NASA), specifically, in developing a subsystems analysis and technology validation team comprised of former spacecraft development personnel. Human factor considerations are investigated from initial concept/vision formulation; through operational process development; personnel test and training; to initial uplink product development and test support. Emphasis has been placed on challenges and applied or recommended solutions, so as to provide opportunities for future programs and projects to address and disposition potential issues and concerns as early as possible to reap the benefits associated with learning from other's past experiences.

Basilio, Ralph R.

Approximate reasoning using terminological models

Term Subsumption Systems (TSS) form a knowledge-representation scheme in AI that can express the defining characteristics of concepts through a formal language that has a well-defined semantics and incorporates a reasoning mechanism that can deduce whether one concept subsumes another. However, TSS's have very limited ability to deal with the issue of uncertainty in knowledge bases. The objective of this research is to address issues in combining approximate reasoning with term subsumption systems. To do this, we have extended an existing AI architecture (CLASP) that is built on the top of a term subsumption system (LOOM). First, the assertional component of LOOM has been extended for asserting and representing uncertain propositions. Second, we have extended the pattern matcher of CLASP for plausible rule-based inferences. Third, an approximate reasoning model has been added to facilitate various kinds of approximate reasoning. And finally, the issue of inconsistency in truth values due to inheritance is addressed using justification of those values. This architecture enhances the reasoning capabilities of expert systems by providing support for reasoning under uncertainty using knowledge captured in TSS. Also, as definitional knowledge is explicit and separate from heuristic knowledge for plausible inferences, the maintainability of expert systems could be improved.

Yen, John

Evidence Arguments for Using Formal Methods in Software Certification

We describe a generic approach for automatically integrating the output generated from a formal method/tool into a software safety assurance case, as an evidence argument, by (a) encoding the underlying reasoning as a safety case pattern, and (b) instantiating it using the data produced from the method/tool. We believe this approach not only improves the trustworthiness of the evidence generated from a formal method/tool, by explicitly presenting the reasoning and mechanisms underlying its genesis, but also provides a way to gauge the suitability of the evidence in the context of the wider assurance case. We illustrate our work by application to a real example-an unmanned aircraft system- where we invoke a formal code analysis tool from its autopilot software safety case, automatically transform the verification output into an evidence argument, and then integrate it into the former.

Argumentation

Apex Reference Manual 3.0 Beta

Apex is a toolkit for constructing software that behaves intelligently and responsively in demanding task environments. Reflecting its origin at NASA where Apex continues to be developed, current applications include: a) Providing autonomous mission management and tactical control capabilities for unmanned aerial vehicles including an autonomous surveillance helicopter and a simulation prototype of an unmanned fixed-wing aircraft to be used for wildfire mapping; b) Simulating human air traffic controllers, pilots and astronauts to help predict how people might respond to changes in equipment or procedures; and c) Predicting the precise duration and sequence of routine human behaviors based on a human-computer interaction engineering technique called CPM-GOMS. Among Apex s components are a set of implemented reasoning services, such as those for reactive planning and temporal pattern recognition; a software architecture that embeds and integrates these services and allows additional reasoning elements to be added as extensions; a formal language for specifying agent knowledge; a simulation environment to facilitate prototyping and analysis; and Sherpa, a set of tools for visualizing autonomy logic and runtime behavior. In combination, these are meant to provide a flexible and usable framework for creating, testing, and deploying intelligent agent software. Overall, our goal in developing Apex is to lower economic barriers to developing intelligent software agents. New ideas about how to extend or modify the system are evaluated in terms of their impact in reducing the time, expertise, and inventiveness required to build and maintain applications. For example, potential enhancements to the AI reasoning capabilities in the system are reviewed not only for usefulness and distinctiveness, but also for their impact on the readability and general usability of Apex s behavior representation language (PDL) and on the transparency of resulting behavior. A second central part of our approach is to iteratively refine Apex based on lessons learned from as diverse a set of applications as possible. Many applications have been developed by users outside the core development team including engineers, researchers, and students. Usability is thus a central concern for every aspect of Apex visible to a user, including PDL, Sherpa, the Apex installation process, APIs, and user documentation. Apex users vary in their areas of expertise and in their familiarity with autonomy technology. Focusing on usability, a development philosophy summarized by the project motto "Usable Autonomy," has been important part of enabling diverse users to employ Apex successfully and to provide feedback needed to guide iterative, user-centered refinement.

Freed, Michael A.

Single-Molecule Electron Transport in Peptoids

Peptoids are structural analogs of peptides in which side chains are appended to the backbone nitrogen rather than the α-carbon. The sequence-defined modularity of peptoids enables precise control over structure−function relationships, enabling applications in energy storage and biomedical materials. Despite recent progress, the role of sequence and conformation on electron transport in peptoid molecules is not fully understood. Here, we synthesize a library of peptoid oligomers and characterize their molecular electronic properties using the scanning tunneling microscope-break junction (STM-BJ) technique. Our results show well-defined electron transport behavior for peptoid sequences containing aromatic side groups lacking hydrogen bonds (H-bonds) and without chemical substitutions at the N−C α position. This behavior fundamentally differs from electron transport in peptides, where H-bond interactions give rise to higher conductance states. All-atom molecular dynamics (MD) simulations are used to understand the conformational heterogeneity of peptoids, and molecular conformations obtained from MD simulations are used in quantum mechanical calculations based on the nonequilibrium Green’s function−density functional theory (NEGF-DFT) formalism. In all cases, computational results are in reasonable qualitative agreement with experiments. Our work demonstrates that the conductance behavior of peptoids depends on monomer identity, including side-chain aromaticity and substitution at the N−C α position. Overall, this work provides new insights into the structure−function relationships governing electron transport in peptoid-based materials and establishes design rules for peptoid-based molecular junctions.

Charge transport

Slice-Based Formal Specification Measures -- Mapping Coupling and Cohesion Measures to Formal Z

This paper demonstrates that existing slice-based measures can reasonably be mapped to the field of state-based specification languages. By making use of Z specifications this contribution renews the idea of slice-profiles and derives coupling and cohesion measures for them. The measures are then assessed by taking a critical look at their sensitiveness in respect to modifications on the specification source. The presented study shows that slice-based coupling and cohesion measures have the potential to be used as quality indicators for specifications as they reflect the changes in the structure of a specification as accustomed from their program-related pendants.

Bollin, Andreas

Defining the IEEE-854 floating-point standard in PVS

A significant portion of the ANSI/IEEE-854 Standard for Radix-Independent Floating-Point Arithmetic is defined in PVS (Prototype Verification System). Since IEEE-854 is a generalization of the ANSI/IEEE-754 Standard for Binary Floating-Point Arithmetic, the definition of IEEE-854 in PVS also formally defines much of IEEE-754. This collection of PVS theories provides a basis for machine checked verification of floating-point systems. This formal definition illustrates that formal specification techniques are sufficiently advanced that is is reasonable to consider their use in the development of future standards.

Miner, Paul S.

Facility Monitoring: A Qualitative Theory for Sensor Fusion

Data fusion and sensor management approaches have largely been implemented with centralized and hierarchical architectures. Numerical and statistical methods are the most common data fusion methods found in these systems. Given the proliferation and low cost of processing power, there is now an emphasis on designing distributed and decentralized systems. These systems use analytical/quantitative techniques or qualitative reasoning methods for date fusion.Based on other work by the author, a sensor may be treated as a highly autonomous (decentralized) unit. Each highly autonomous sensor (HAS) is capable of extracting qualitative behaviours from its data. For example, it detects spikes, disturbances, noise levels, off-limit excursions, step changes, drift, and other typical measured trends. In this context, this paper describes a distributed sensor fusion paradigm and theory where each sensor in the system is a HAS. Hence, given the reach qualitative information from each HAS, a paradigm and formal definitions are given so that sensors and processes can reason and make decisions at the qualitative level. This approach to sensor fusion makes it possible the implementation of intuitive (effective) methods to monitor, diagnose, and compensate processes/systems and their sensors. This paradigm facilitates a balanced distribution of intelligence (code and/or hardware) to the sensor level, the process/system level, and a higher controller level. The primary application of interest is in intelligent health management of rocket engine test stands.

Figueroa, Fernando

Formal Verification of the Interaction Between Semi-Algebraic Sets and Real Analytic Functions

Semi-algebraic sets and real analytic functions are fundamental concepts in Real Algebraic Geometry and Real Analysis, respectively. These concepts interact in the study of Differential Equations, where the real analytic solution to a differential equation is known to enter or exit a semi-algebraic set in a predicable way. Motivated to enhance the capability to reason about differential equations in the Prototype Verification System (PVS), a formalization of multivariate polynomials, semi-algebraic sets, and real analytic functions is developed. The favorable way that a real analytic function enters and exits a semi-algebraic set is proven. It is further shown that if the function is assumed to be smooth, a slightly weaker assumption than real analytic, these favorable interactions with semi-algebraic sets may fail.

Real analytic functions

Theory of Cation Solvation in the Helmholtz Layer of Li-Ion Battery Electrolytes

The solvation environments of Li + in conventional nonaqueous battery electrolytes, such as LiPF 6 in mixtures of ethylene carbaronate (EC) and ethyl methyl carbonate (EMC), are often used to rationalize transport properties and solid electrolyte interphase (SEI) formation. Solvation environments in the compact electrical double layer (EDL) next to the electrode, also known as the Helmholtz layer, determine (partially) what species can react to form the SEI, with bulk solvation environments often being used as a proxy. Here, we develop and test a theory of cation solvation in the Helmholtz layer of nonaqueous Li-ion battery electrolytes. First, we validate the theory against bulk and diffuse EDL atomistic molecular dynamics (MD) simulations of LiPF 6 EC/EMC mixtures as a function of surface charge, where we find the theory can qualitatively capture the solvation environments. Next, we turn to the Helmholtz layer, where we find the main effect of the solvation structures next to the electrode is an apparent reduction in the number of binding sites between Li + and the solvents, again where we find reasonable agreement with our developed theory. Finally, by solving a simplified version of the theory, we find that the probability of Li + binding to each solvent remains equal to the bulk probability, suggesting that the bulk solvation environments are a reasonable place to start when understanding battery electrolytes. Our developed formalism can be parametrized from bulk MD simulations and used to predict the solvation environments in the Helmholtz layer through reducing the number of available coordination sites, which can be used to determine what could react and form the SEI.

Helmholtz