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At least 505 records · Page 28

Nonlinear sparse Bayesian learning for physics-based models

This paper addresses the issue of overfitting while calibrating unknown parameters of over-parameterized physics-based models with noisy and incomplete observations. Here, a semi-analytical Bayesian framework of nonlinear sparse Bayesian learning (NSBL) is proposed to identify sparsity among model parameters during Bayesian inversion. NSBL offers significant advantages over machine learning algorithm of sparse Bayesian learning (SBL) for physics-based models, such as 1) the likelihood function or the posterior parameter distribution is not required to be Gaussian, and 2) prior parameter knowledge is incorporated into sparse learning (i.e. not all parameters are treated as questionable). NSBL employs the concept of automatic relevance determination (ARD) to facilitate sparsity among questionable parameters through parameterized prior distributions. The analytical tractability of NSBL is enabled by employing Gaussian ARD priors and by building a Gaussian mixture-model approximation of the posterior parameter distribution that excludes the contribution of ARD priors. Subsequently, type-II maximum likelihood is executed using Newton's method whereby the evidence and its gradient and Hessian information are computed in a semi-analytical fashion. We show numerically and analytically that SBL is a special case of NSBL for linear regression models. Subsequently, a linear regression example involving multimodality in both parameter posterior pdf and model evidence is considered to demonstrate the performance of NSBL in cases where SBL is inapplicable. Next, NSBL is applied to identify sparsity among the damping coefficients of a mass-spring-damper model of a shear building frame. These numerical studies demonstrate the robustness and efficiency of NSBL in alleviating overfitting during Bayesian inversion of nonlinear physics-based models.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Data-driven models of nonautonomous systems

Nonautonomous dynamical systems are characterized by time-dependent inputs, which complicates the discovery of predictive models describing the spatiotemporal evolution of the state variables of quantities of interest from their temporal snapshots. When dynamic mode decomposition (DMD) is used to infer a linear model, this difficulty manifests itself in the need to approximate the time-dependent Koopman operators. Our approach is to approximate the original nonautonomous system with a modified system derived via a local parameterization of the time-dependent inputs. The modified system comprises a sequence of local parametric systems, which are subsequently approximated by a parametric surrogate model using the DRIPS (dimension reduction and interpolation in parameter space) framework. The offline step of DRIPS relies on DMD to build a linear surrogate model, endowed with reduced-order bases for the observables mapped from training data. The online step interpolates on suitable manifolds to construct a sequence of iterative parametric surrogate models; the target/test parameter points on these manifolds are specified by a local parameterization of the test time-dependent inputs. Here, we use numerical experimentation to demonstrate the robustness of our method and compare its performance with that of deep neural networks.

97 MATHEMATICS AND COMPUTING↗

Neural chaos: A spectral stochastic neural operator

Building surrogate models for operators with uncertainty quantification capabilities is essential for many engineering applications where randomness–such as variability in material properties, boundary conditions, and initial conditions–is unavoidable. Polynomial Chaos Expansion (PCE) is widely recognized as a go-to method for constructing stochastic surrogates in both intrusive and non-intrusive ways, and it has recently been used in the context of operator learning. However, its application becomes challenging for complex or high-dimensional processes, as achieving accuracy requires higher-order polynomials, which can increase computational demand and/or the risk of overfitting. Furthermore, PCE requires specialized treatments to manage random variables that are not independent, and these treatments may be problem-dependent or may fail with increasing complexity. Here, in this work, we adopt the same formalism as the spectral expansion used in PCE; however, we replace the classical polynomial basis functions with neural network (NN) basis functions to leverage their expressivity. To achieve this, we propose an algorithm that identifies NN-parameterized basis functions in a purely data-driven manner, without any prior assumptions about the joint distribution of the random variables involved, whether independent or dependent, or about their marginal distributions. The proposed algorithm identifies each NN-parameterized basis function sequentially, ensuring they are orthogonal with respect to the data distribution. The basis functions are constructed directly on the joint stochastic variables without requiring a tensor product structure or assuming independence of the random variables. This approach may offer greater flexibility for complex stochastic models, while simplifying implementation compared to the tensor product structures typically used in PCE to handle random vectors. This is particularly advantageous given the current state of open-source packages, where building and training neural networks can be done with just a few lines of code and extensive community support. We demonstrate the effectiveness of the proposed scheme through several numerical examples of varying complexity and provide comparisons with classical PCE.

Polynomial chaos expansion↗

SWAT model application for evaluating agricultural conservation practice effectiveness in reducing phosphorous loss from the Western Lake Erie Basin

Lake Erie is threatened by eutrophication and harmful algal blooms due to excess nutrient loading from agricultural sources. Agricultural conservation practices (ACPs) have been developed and implemented to reduce nutrient losses but estimating ACP effectiveness is challenging. The Soil and Water Assessment Tool (SWAT) has been used to investigate ACP effectiveness for water quality improvement. Many SWAT applications have been developed by different investigators to evaluate ACP effectiveness for reducing nutrient, particularly phosphorus (P), loading in the agriculturally-dominated Western Lake Erie Basin (WLEB). Our objective is to establish what has been achieved by past modeling research and make suggestions for future applications and improvements. We synthesized the findings of 28 SWAT modeling studies within the WLEB. Models generally performed satisfactorily against accepted criteria for streamflow and sediment, but performance for P loads, like soluble reactive P, was mostly “unsatisfactory”. The “unsatisfactory” performance maybe due to imperfections and idealizations in model formulations and/or parameterization. Thus, simulations of P transport and transformation processes need improvement. In addition, model parameter selection is the key part of model set-up. Most SWAT modeling studies used default values during initial set-up, then performed calibration and validation. It was found that the calibrated P related parameter values varied widely across different studies, even within the same watershed with some values unrealistic for the study areas. The phenomena of different combinations of model parameters producing similar outputs indicates equifinality. Equifinality in the baseline model may impact results when ACPs are incorporated. Furthermore, the unrealistic values used in ACP assessment undermine the credibility of ACP effectiveness. Future model applications should try to re-examine the calibrated P parameters and make sure they are realistic for the study area as well as reduce equifinality by constraining the model with characterization of watershed conditions, better understanding of hydrologic processes, and parameter values based on real-world observations. As a result, future model applications should focus on improving P transport and transformation processes, using measured watershed characteristics for parameterization, and improving reflections of climate change, which could result in more accurate assessments of ACP effectiveness to meet targeted goals.

54 ENVIRONMENTAL SCIENCES↗

A large-scale comparison of Artificial Intelligence and Data Mining (AI&DM) techniques in simulating reservoir releases over the Upper Colorado Region

In recent years, the Artificial Intelligence and Data Mining (AI&DM) models have become popular tools in assisting various aspects of reservoir operation. However, the practical uses are still rarely reported. Comparison experiment of many AI&DM models over a large number of reservoir cases is particularly valuable to help reservoir operators first examine the usefulness and transferability of different AI&DM models, and then identify the most stable and reliable AI&DM model in assist of various decision-making processes. In this study, a total of 12 AI&DM models with different parameterizations and simulation scenarios are comprehensively tested out and compared in simulating the controlled reservoir outflows of 33 reservoir cases over the Upper Colorado Region, United States. Results show that the Random Forecast and the Long-Short-Term-Memory model could consistently derive the best statistical performance than other models under the baseline simulation scenario. The employed AI&DM models could obtain satisfactory statistical interquartile ranges (25–75%) between [0.6–0.9], [0.3–0.8], and [0.2–0.8], for CORR, NSE, and KGE measurements, respectively, and [1.5–6.5], [–15 to 20], and [0.5–8.5] for the normalized RMSE, PBIAS and RSR measurements, respectively. Results also show Multi-Layer Perceptron model and Extreme Gradient Boosting Tree Algorithm produced more stable and superior performance than other models under more complex input scenarios. We also found that the performance of different AI&DM models are closely relevant to the reservoir elevations, sizes, and functionalities. Discussions were made about the sensitivity of AI&DM models’ parameterizations and the key advantages of AI&DM models over the rule-based reservoir models. We further identify that the main advantage of AI&DM models is the flexibility in designing input structures, whereas the rule-based simulation model is rather limited. Future studies were suggested regarding the best way reservoir operators and researchers could use, select, and apply different AI&DM models in simulating reservoir releases under different natural and modeling environments. Finally, this comparison study also serves as a reference and a piece of groundwork for further promoting the practical uses of AI&DM models in assisting reservoir operation.

54 ENVIRONMENTAL SCIENCES↗

Application of the immobilized low-activity waste glass corrosion model to the static dissolution of 24 statistically-designed alkali-borosilicate waste glasses

Glass corrosion models that capture the complex mechanisms of the glass-water reaction enable the prediction of nuclear waste glass durability in disposal scenarios. Parameterization of such models is challenging because of the need to capture changes in corrosion behavior with time, reaction conditions, and glass composition. In this report we describe and employ the immobilized low activity waste (ILAW) glass corrosion model (IGCM) in geochemical simulations of static dissolution tests, at two temperatures (40 °C and 90 °C), for a matrix of 24 enhanced low activity waste (eLAW) glasses statistically designed to cover a processable composition space defined by 8 major glass components (Al 2 O 3 , B 2 O 3 , CaO, Na 2 O, SiO 2 , SnO 2 , ZrO 2 , and Others as defined in the text). The IGCM includes a first-order chemical affinity term and an ion-exchange term that represents the net exchange of Na+ ions in the pristine glass with protons in aqueous solution. Constant, time-dependent, and time- and pH-dependent functional forms of the ion-exchange term are evaluated to reproduce the change in corrosion behavior with time in saturated, static dissolution tests. The agreement with measured aqueous concentrations of the main glass components (B, Na, and Si) improved significantly upon addition of a time-dependent term, which therefore constitutes a simple representation of the glass-water reaction progress. Due to the limited changes in pH in the static dissolution tests, past a short initial period of rapid increase, addition of a pH dependent term did not appreciably improve the fits, indicating that comprehensive model parameterization requires more than one type of glass corrosion test to capture a wide range of solution chemistries. IGCM parameters were found to be dependent on glass composition, and the parameter sets generated in this work will enable the development of composition–parameter correlation models that offer the promise of predicting IGCM parameters, and thus glass corrosion behavior, solely based on glass composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ab-initio informed cluster dynamics simulation of self- and Xe diffusivity in uranium mononitride under irradiation

Uranium mononitride (UN) is one of the ceramic nuclear fuel alternatives to oxide fuels considered for light water reactor and advanced reactor designs, as it presents significant advantages such as high uranium density (better economics) and high thermal conductivity and melting point (increased safety). Self- and fission gas diffusivities need to be better understood, given that they influence key fuel performance phenomena like swelling and fission gas release. Recently, radiation enhanced diffusivity was investigated in UN by means of cluster dynamics simulations relying on empirical potential-based parameterizations, the reliability of which highly depends on the interatomic potential accuracy. Here, in this work, we refine this approach by determining, using ab-initio calculations, the properties of defect clusters containing vacancies, self-interstitials and Xe impurities. We also consider larger clusters than previous studies. The obtained dataset (formation enthalpies, entropies, and migration barriers) is used to parameterize a cluster dynamics model of mobile clusters, and to calculate the defect cluster concentrations under irradiation. This gives us access to the radiation enhanced self- and fission gas diffusivities. Although the resulting diffusivities are close to the values reported in the literature, we find important qualitative differences in the diffusion mechanisms. Capturing the correct mechanisms is crucial to properly describe the chemistry and fission rate dependence of the model.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A Kinetic Model of the Long-Term Corrosion of Glass-Ceramic Materials

Multiphase waste forms show promise for increased waste loading and for the ability to dispose of contaminated solid and particulate waste through direct densification. However, achieving predictive capability for long-term durability of multiphase waste forms, and thus assessing their possible deployment, requires expanding the current, limited knowledge base. Here, we describe the development of a corrosion model of a two-phase waste form consisting of crystals of known volume fraction embedded in a glass matrix. This model accounts for the dissolution of both the crystalline and glass phases as well as the hydration of the glass phase through an ion exchange reaction. Because of the large difference in solubility between the two phases, the reactive surface of the crystalline phase is a function of the extent of dissolution of the glass phase in this model. Model parameterization was performed using corrosion data, such as from single-pass flow-through tests, for the individual phases. The parameterized corrosion model was evaluated against static dissolution test data for a glass-ceramic multiphase waste form. This evaluation demonstrated the model’s ability to reproduce the time-dependent release of key tracers of glass and crystalline phase dissolution. Hence, the development of a kinetic model provides a pathway for long-term durability predictions and thus the use of multiphase waste forms in nuclear cleanup missions.

Kerisit, Sebastien N.↗

Modelica-based system modeling for studying control-related faults in chiller plants and boiler plants serving large office buildings

System modeling is critical when studying operation faults in chiller plants and boiler plants. However, current fault models have difficulties faithfully representing the operation of chiller plants and boiler plants under the effects of those faults, especially the control-related ones. In this study, we present a systematic method to develop high-fidelity models for approximating the behaviors of chiller plants and boiler plants under faulty conditions. Compared to existing ones, the resulting fault models have two advantages: first, they better characterize the dynamic patterns in the system operation. In those models, control architecture and control logic are faithfully implemented. Thus, they can be used to study control-related faults, such as incorrect staging control due to sensor bias and mistuned feedback control. Second, they are readily extensible and can support large-scale investigations to explore different faulty conditions/scenarios. Those models are established in a hierarchical structure while modules in each layer can be redeclared and parameterized at upper layers. In such a case, modifications to the models can be realized through model modifiers and the process can be easily streamlined with scripts. We applied the proposed models in a comprehensive fault impact evaluation of the 13 control-related faults of chiller and boiler plants. In this evaluation, the proposed plant model is coupled with the EnergyPlus thermal load model to study the impact of various faulty scenarios. Based on the evaluation results, we identified the faults that have the most significant impacts on the operation of the chiller and boiler plants, respectively. We also found that the relationship between the impacts of the studied faults and the severity level of the faults are highly non-linear

Huang, Sen↗

Reduced order models for thermal radiative transfer problems based on moment equations and data-driven approximations of the Eddington tensor

Here a new group of structure and asymptotic preserving reduced-order models (ROMs) for multidimensional nonlinear thermal radiative transfer (TRT) problems is presented. They are formulated by means of the nonlinear projective approach and data compression techniques. The nonlinear projection is applied to the Boltzmann transport equation (BTE) to derive a hierarchy of low-order moment equations. Approximation of the Eddington tensor that provides exact closure for the system of moment equations is found with projection-based data-driven methodologies. These include the (i) proper orthogonal decomposition (POD), (ii) dynamic mode decomposition (DMD) and (iii) a variant of the DMD. A parameterization is derived for this ROM for the temperature of radiation incoming to the problem domain (the radiation drive temperature). This parameterization is informed from results of a dimensionless study of the TRT problem. Analysis of the ROMs is performed on the classical Fleck-Cummings TRT multigroup test problem in 2D geometry with a radiation-driven Marshak wave. Numerical results are presented to demonstrate the performance of these ROMs for the simulation of evolving radiation and heat waves. Results show these models to be sufficiently accurate for practical computations with rather low-rank representations of the Eddington tensor. As the rank of the approximation is increased, the errors of solutions generated by the ROMs gradually decreases.

42 ENGINEERING↗

Impact of boundary layer simulation on predicting radioactive pollutant dispersion: a case study for HANARO Research Reactor using the WRF-MMIF-CALPUFF modeling system

Wind plays an important role in cases of unexpected radioactive pollutant dispersion, deciding distribution and concentration of the leaked substance. The accurate prediction of wind has been challenging in numerical weather prediction models, especially near the surface because of the complex interaction between turbulent flow and topographic effect. As such, in this study, we investigated the characteristics of atmospheric dispersion of radioactive material (i.e. 137 Cs) according to the simulated boundary layer around the HANARO research nuclear reactor in Korea using the Weather Research and Forecasting (WRF)-Mesoscale Model Interface (MMIF)-California Puff (CALPUFF) model system. We examined the impacts of orographic drag on wind field, stability calculation methods, and planetary boundary layer parameterizations on the dispersion of radioactive material under a radioactive leaking scenario. We found that inclusion of the orographic drag effect in the WRF model improved the wind prediction most significantly over the complex terrain area, leading the model system to estimate the radioactive concentration near the reactor more conservatively. We also emphasized the importance of the stability calculation method and employing the skillful boundary layer parameterization to ensure more accurate low atmospheric conditions, in order to simulate more feasible spatial distribution of the radioactive dispersion in leaking scenarios.

54 ENVIRONMENTAL SCIENCES↗

Assessing observational constraints on dark energy

Observational constraints on time-varying dark energy (e.g., quintessence) are commonly presented on a w 0 –w a plot that assumes the equation of state of dark energy strictly satisfies w(z) = w 0 + w a z/(1 + z) as a function of the redshift z. Recent observations favor a sector of the w 0 –w a plane in which w 0 > –1 and w 0 + w a < –1, suggesting that the equation of state underwent a transition from violating the null energy condition (NEC) at large z to obeying it at small z. In this paper, we demonstrate that this impression is misleading by showing that simple quintessence models satisfying the NEC for all z predict an observational preference for the same sector. We also find that quintessence models that best fit observational data can predict a value for the dark energy equation of state at present that is significantly different from the best-fit value of w 0 obtained assuming the parameterization above. In addition, the analysis reveals an approximate degeneracy of the w 0 –w a parameterization that explains the eccentricity and orientation of the likelihood contours presented in recent observational studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Characterizing model uncertainties in simulated coast-to-offshore wind over the northeast U.S. using multi-platform measurements from the TCAP field campaign

Numerical weather prediction (NWP) models, such as the Weather Research and Forecasting (WRF) model, are widely used to provide estimates of the offshore wind energy resource owing to their large spatial coverage compared to available observations. Nevertheless, spatiotemporal distribution of model biases is highly dependent on factors including model configuration, location, and the interplay of multi-scale physical processes. Here, in this study, we focus on the characterization of model uncertainties in simulated coast-to-offshore winds over the northeast U.S., by varying sea surface temperature (SST) forcings, surface layer (SL) and planetary boundary layer (PBL) parameterizations, as well as identifying biases that may be directly passed from initial and boundary conditions. Multiple measurements, including aircraft data collected during the U.S. Department of Energy's Two-Column Aerosol Project (TCAP) experiment, are used to constrain the model results and facilitate quantitative comparisons. Our analysis indicates while SST forcing has notable impacts on simulated air temperature and moisture within PBL, the modeled winds are in general more sensitive to the choices of SL and PBL physics than to SST. The model’s forcing data not only controls the vertical dependence of wind speed errors, but also alters regional variability in wind speed’s spatial correlation. Bias comparisons between ERA5 reanalysis and ensemble simulations revealed significant similarity, particularly in wind speed biases during winter, underscoring their dependency on initial and boundary conditions. Coastal and offshore near-surface wind speed biases tend to exhibit much higher similarity in winter than in summer due to the presence of much stronger and more persistent synoptic wind conditions. This study highlights the importance of accurate atmospheric forcing and parameterization choices in improving wind forecasts and suggests the potential for extrapolating coastal wind biases to offshore locations, aiding wind energy forecasting and informing the Wind Forecast Improvement Project-3 (WFIP3).

17 WIND ENERGY↗

Plant litter traits control microbial decomposition and drive soil carbon stabilization

Efforts to manage soils for carbon (C) sequestration remain limited by our understanding of how differences in plant traits and microbial traits mechanistically drive soil organic C (SOC) storage. Addressing this uncertainty is particularly critical in bioenergy agriculture, due to its potential to enhance soil C and provide a C neutral fuel. As such, we examined differences between two contrasting feedstocks, Zea mays (corn) and Miscanthus x giganteus (miscanthus), in the ability of their litter to form new chemically resistant particulate SOC vs. physically protected mineral associated SOC and used this data to improve the parameterization of a microbial SOC model. We tested a hypothesized conceptual model whereby easy to decompose corn litters drive greater microbial carbon use efficiency (CUE) and the formation of more mineral associated SOC over particulate SOC than more complex miscanthus litters. To do this, we performed a soil microcosm experiment where we added 13 C enriched aboveground and belowground litters to soils and traced the fate of the 13 C into microbial respiration and SOC pools. We found that corn litters promoted higher microbial CUE (0.37) than miscanthus litters (0.24). In turn, corn litter formed approximately 50% more mineral associated SOC than miscanthus litters. Similarly, structurally complex root litters promoted a lower CUE and formed less mineral associated SOC than leaf and shoot litters for both crops. When we used our data to parameterize the SOC model, we found that modelling microbial trait differences uniquely allowed the model to capture the fate of litter C in SOC. Collectively, we found a robust link between litter quality, microbial efficiency, and the formation of SOC. This link bridges the empirical uncertainty in how different crops can form new soil C and provides an empirical basis for modelling SOC transformations.

59 BASIC BIOLOGICAL SCIENCES↗

Interrelationships among methods of estimating microbial biomass across multiple soil orders and biomes

Understanding the role of soil microbes is critical to ecosystem processes, and more thorough comparisons of measurement proxies for soil microbial biomass could broaden the inclusion of explicit microbial parameterization in soil carbon cycling and earth system models. We measured physical, chemical, and biological data from eight soil orders representing 11 major biomes and four climate regions. Four prominent methods to measure microbial abundance—chloroform fumigation extraction (CFE), total DNA yield, gene copy number by quantitative polymerase chain reaction (GCN), and phospholipid fatty acids (PLFA)—were compared to assess their relationships with each other and with soil characteristics. Correlations were observed when comparing methods, with CFE correlating strongly with total DNA yield, GCN, and PLFA; CFE with bacterial GCN and bacterial PLFA; and to a lesser extent, total PLFA and total DNA yield. Correlations improved with the removal of organic soils (Histosols, Gelisols). Comparisons involving extracted DNA were improved by correcting for clay content, due to DNA extraction inefficiencies in clay-rich soils. Correlations involving fungi (PLFA or GCN) were always less significant. These methods could serve as reliable, inter-relatable proxies for the estimation of total soil microbial biomass while recognizing that the proxies are less effective at parsing differences between bacteria and fungi. Here, we provide specific equations to relate measures of soil microbial biomass by these four different methods to enable microbial models to utilize a greater diversity of observed data sources in parameterizations and simulations. Caveats for the equations and their values are also discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Improved representation of laminar and turbulent sheet flow in subglacial drainage models

Subglacial hydrology models struggle to reproduce seasonal drainage patterns that are consistent with observed subglacial water pressures and surface velocities. We modify the standard sheet-flow parameterization within a coupled sheet–channel subglacial drainage model to smoothly transition between laminar and turbulent flow based on the locally computed Reynolds number in a physically consistent way (the ‘transition’ model). We compare the transition model to standard laminar and turbulent models to assess the role of the sheet-flow parameterization in reconciling observed and modelled water pressures under idealized and realistic forcing. Relative to the turbulent model, the laminar and transition models improve seasonal simulations by increasing winter water pressure and producing a more prominent late-summer water pressure minimum. In contrast to the laminar model, the transition model remains consistent with its own internal assumptions across all flow regimes. Based on the internal consistency of the transition model and its improved performance relative to the standard turbulent model, we recommend its use for transient simulations of subglacial drainage.

54 ENVIRONMENTAL SCIENCES↗

Quantifying and Modeling the Impact of Phase State on the Ice Nucleation Abilities of 2-Methyltetrols as a Key Component of Secondary Organic Aerosol Derived from Isoprene Epoxydiols

Organic aerosols (OAs) may serve as ice-nucleating particles (INPs), impacting the formation and properties of cirrus clouds when their phase state and viscosity are in the semisolid to glassy range. However, there is a lack of direct parameterization between aerosol viscosity and their ice nucleation capabilities. In this study, we experimentally measured the ice nucleation rate of 2-methyltetrols (2-MT) aerosols, a key component of isoprene-epoxydiol-derived secondary organic aerosols (IEPOX-SOA), at different viscosities. These results demonstrate that the phase state has a significant impact on the ice nucleation abilities of OA under typical cirrus cloud conditions, with the ice nucleation rate increasing by 2 to 3 orders of magnitude when the phase state changes from liquid to semisolid. An innovative parametric model based on classical nucleation theory was developed to directly quantify the impact of viscosity on the heterogeneous nucleation rate. This model accurately represents our laboratory measurement and can be implemented into climate models due to its simple, equation-based form. Based on data collected from the ACRIDICON-CHUVA field campaign, our model predicts that the INP concentration from IEPOX-SOA can reach the magnitude of 1 to tens per liter in the cirrus cloud region impacted by the Amazon rainforest, consistent with recent field observations and estimations. This novel parameterization framework can also be applied in regional and global climate models to further improve representations of cirrus cloud formation and associated climate impacts.

2-methyltetrol↗

Capturing Deuteration Effects in a Molecular Mechanics Force Field: Deuterated THF and the THF–Water Miscibility Gap

Deuteration is a common chemical modification used in conjunction with experiments such as neutron scattering, NMR, and Fourier-transform infrared for the study of molecular systems. Under the Born–Oppenheimer (BO) approximation, while the underlying potential energy surface remains unchanged by isotopic substitutions, isotopic substitution still alters intramolecular vibrations, which in turn may alter intermolecular interactions. Molecular mechanics (MM) force fields used in classical molecular dynamics simulations are assumed to represent local approximations of the BO potential energy surfaces, and hence, MD simulations using simple isotopic mass substitutions should capture BO-compatible isotope effects. However, standard MM force-field parameterizations do not directly fit to the local harmonic quantum mechanical (QM) Hessian that describes the BO surface, but rather to QM normal-modes and/or mass-dependent internal-coordinate derived distortion energies. In this study, using tetrahydrofuran (THF)–water mixtures as our model system, we show that not only does a simple mass-substitution approach fail to capture an experimentally characterized deuteration effect (the loss of the closed-loop miscibility gap associated with the complete deuteration of THF) but also it is necessary to generate new MM force-field parameters that correctly describe isotopic dependent vibrations to capture the experimental deuteration effect. We show that the origin of this failure is a result of using mass-dependent features to fit the THF MM force field, which unintentionally biases the bonded terms of the force field to represent only the isotopologue used during the original force-field parameterization. In addition, we make use of our isotopologue-corrected force field for D 8 THF to examine the molecular origins of the isotope-dependent loss of the THF–water miscibility gap.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗