Stochastic Parameterization to Represent Variability and Extremes in Climate Modeling
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Langan, Roisin T↗
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A Model Intercomparison Study of Aerosol‐Cloud‐Turbulence Interactions in a Cloud Chamber: 1. Model Results
This study presents the first model intercomparison of aerosol‐cloud‐turbulence interactions in a controlled cloudy Rayleigh‐Bénard Convection chamber environment, utilizing the Pi Chamber at Michigan Technological University. We analyzed simulated cloud chamber‐averaged statistics of microphysics and thermodynamics in a warm‐phase, cloudy environment under steady‐state conditions at varying aerosol injection rates. Simulation results from seven distinct models (DNS, LES, and a 1D turbulence model) were compared. Our findings demonstrate that while all models qualitatively capture observed trends in droplet number concentration, mean radius, and droplet size distributions at both high and low aerosol injection rates, significant quantitative differences were observed. Notably, droplet number concentrations varied by over two orders of magnitude between models for the same injection rates, indicating sensitivities to the model treatments in droplet activation and removal and wall fluxes. Furthermore, inconsistencies in vertical relative humidity profiles and in achieving steady‐state liquid water content suggest the need for further investigation into the mechanisms driving these variations. Despite these discrepancies, the models generally reproduced consistent power‐law relationships between the microphysical variables. This model intercomparison underscores the importance of controlled cloud chamber experiments for validating and improving cloud microphysical parameterizations. Recommendations for future modeling studies are also highlighted, including constraining wall conditions and processes, investigating droplet/aerosol removal (including sidewall losses), and conducting simplified experiments to isolate specific processes contributing to model divergence and reduce model uncertainties.
54 ENVIRONMENTAL SCIENCES↗
Evaluation of Planetary Boundary Layer Simulation in GFDL Atmospheric General Circulation Models
This study describes the performance of two Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric general circulation models (AGCMs) in simulating the climatologies of planetary boundary layer (PBL) parameters, with a particular focus on the diurnal cycles. The two models differ solely in the PBL parameterization: one uses a prescribed K-profile parameterization (KPP) scheme with an entrainment parameterization, and the other employs a turbulence kinetic energy (TKE) scheme. The models are evaluated through comparison with the reanalysis ensemble, which is generated from European Centre for Medium-Range Weather Forecasts (ECMWF) twentieth-century reanalysis (ERA-20C), ERA-Interim, NCEP CFSR, and NASA MERRA, and the following systematic biases are identified. The models exhibit widespread cold biases in the high latitudes, and the biases are smaller when the KPP scheme is used. The diurnal cycle amplitudes are underestimated in most dry regions, and the model with the TKE scheme simulates larger amplitudes. For the near-surface winds, the models underestimate both the daily means and the diurnal amplitudes; the differences between the models are relatively small compared to the biases. The role of the PBL schemes in simulating the PBL parameters is investigated through the analysis of vertical profiles. The Sahara, which is suitable for focusing on the role of vertical mixing in dry PBLs, is selected for a detailed analysis. It reveals that compared to the KPP scheme, the heat transport is weaker with the TKE scheme in both convective and stable PBLs as a result of weaker vertical mixing, resulting in larger diurnal amplitudes. Lack of nonlocal momentum transport from the nocturnal low-level jets to the surfaces appears to explain the underestimation of the near-surface winds in the models.
58 GEOSCIENCES↗
Improving Convection Parameterization Using ARM Observations and NCAR Community Atmosphere Model
We made significant contribution to the ASR program in this funding cycle by better representing convective processes in GCMs based on knowledge gained from analysis of ARM/ASR observations. In addition, our work led to a much improved understanding of the interaction among aerosol, convection, clouds and climate in GCMs. Below is a highlight of our achievements.
15 GEOTHERMAL ENERGY↗
Scrutinizing entrainment and mass flux closures in shallow cumulus parameterizations using cloud-radar observations and large-eddy simulation (Final Report)
Representing warm, shallow clouds is a challenge for Global Climate Models, which leads to uncertainty in model projections of future climate. Our study was particularly concerned with how climate models represent the effects of shallow, non-precipitating cumulus clouds. Climate models must make certain assumptions when representing low clouds such as how much dry air from outside the cloud is mixed into the warm, moist cloud updraft. This process is called “entrainment” and tends to weaken the cloud updraft and dry out the cloud, compared to a theoretical cloud with no mixing. This project was a joint observational and modeling study to derive estimates of entrainment from field observations and use high-resolution modeling to evaluate the assumptions used in climate model representations of shallow cumulus. Our research took advantage of a wide variety of Department of Energy measurements from fixed climate-monitoring locations over the Southern Great Plains of the U.S. and the in the Eastern North Atlantic, along with short-term field projects (MAGIC, CAP–MBL, ACE–ENA). During the project, the PI maintained regular collaborations with Department of Energy Scientists at Brookhaven and Argonne National Laboratories. The project funded two students, who both obtained their M.S. in Atmospheric Science and are currently in the Atmospheric Science Ph.D. program. Both were lead authors on research papers funded by this grant.
54 ENVIRONMENTAL SCIENCES↗
Urban weather modeling using WRF: linking physical assumptions, code implementation, and observational needs
The Weather Research and Forecasting (WRF) model includes urban schemes that simulate the influence of urban surfaces on the atmosphere using parameterizations for flux, and radiative exchanges. Three core schemes – the Bulk urban parameterization, Single-Layer Urban Canopy Model (SLUCM), and Multi-Layer Urban Canopy Model (MLUCM) – represent increasing levels of complexity. Although the parameterizations within these urban schemes are described in the literature, their specific implementation remains poorly documented, thus slowing down model development efforts. This manuscript provides a roadmap to the three urban schemes in WRF version 4.5.2, presenting equations using the same symbols as in the model code, along with references to code lines, and including graphics and explanations that connect the code to its physical foundations. Our thorough review of the urban parameterizations implemented in WRF version 4.5.2 highlighted a handful of parameters that may introduce discontinuities in simulations: (i) in the SLUCM, a 1 mm h −1 rain rate threshold is employed to switch between two minimum moisture availability parameterizations, thus impacting latent heat flux calculations; (ii) in the SLUCM a threshold is used to partition shortwave radiation into direct and diffuse components; (iii) in all three urban schemes, the bulk Richardson number is employed to select the similarity function, which influences the vertical distribution of heat and momentum. We also identified a highly simplified treatment of the radiative balance on roof surfaces. The implications of these simplifications can be assessed through targeted observations across relevant conditions, including varying precipitation rates, cloud cover, and transitions between stability regimes. Furthermore, the widespread application of the Monin-Obukhov similarity theory in these urban schemes warrants model evaluation under highly stable and unstable conditions and in heterogeneous urban settings with variable land cover and building heights on scales finer than model resolution. To address these challenges, we offer guidance on observational strategies, emphasizing the need for multi-parametric measurements to capture potential compensating biases and multi-height measurements that align with the levels where quantities are diagnostic and prognosed in the model (i.e., the lowest atmospheric level of the WRF model). Finally, our inspection of the code revealed implementation bugs that have now been corrected in WRF versions 4.6.0 and 4.6.1. Sensitivity tests over the Atlanta urban area show that these corrections affect surface temperatures, underscoring the importance of performing rigorous documentation and verification of the implementation of parameterizations in model code.
54 ENVIRONMENTAL SCIENCES↗
Landscape-scale consequences of differential tree mortality from catastrophic wind disturbance in the Amazon
Wind disturbance can create large forest blowdowns, which greatly reduces live biomass and adds uncertainty to the strength of the Amazon carbon sink. Observational studies from within the central Amazon have quantified blowdown size and estimated total mortality but have not determined which trees are most likely to die from a catastrophic wind disturbance. Also, the impact of spatial dependence upon tree mortality from wind disturbance has seldom been quantified, which is important because wind disturbance often kills clusters of trees due to large treefalls killing surrounding neighbors. We examine (1) the causes of differential mortality between adult trees from a 300-ha blowdown event in the Peruvian region of the northwestern Amazon, (2) how accounting for spatial dependence affects mortality predictions, and (3) how incorporating both differential mortality and spatial dependence affect the landscape level estimation of necromass produced from the blowdown. Standard regression and spatial regression models were used to estimate how stem diameter, wood density, elevation, and a satellite-derived disturbance metric influenced the probability of tree death from the blowdown event. The model parameters regarding tree characteristics, topography, and spatial autocorrelation of the field data were then used to determine the consequences of non-random mortality for landscape production of necromass through a simulation model. Tree mortality was highly non-random within the blowdown, where tree mortality rates were highest for trees that were large, had low wood density, and were located at high elevation. Of the differential mortality models, the non-spatial models overpredicted necromass, whereas the spatial model slightly underpredicted necromass. When parameterized from the same field data, the spatial regression model with differential mortality estimated only 7.5% more dead trees across the entire blowdown than the random mortality model, yet it estimated 51% greater necromass. As a result, we suggest that predictions of forest carbon loss from wind disturbance are sensitive to not only the underlying spatial dependence of observations, but also the biological differences between individuals that promote differential levels of mortality.
54 ENVIRONMENTAL SCIENCES↗
Addressing Model Form Error for Time-Dependent Conservation Equations
Model form error of the type considered here is error due to an approximate or incorrect representation of physics by a computational model. Typical approaches to adjust a model based on observed differences between experiment and prediction are to calibrate the model parameters utilizing the observed discrepancies and to develop parameterized additive corrections to the model output. These approaches are generally not suitable if significant physics is missing from the model and the desired quantities of interest for an application are different than those used for calibration. The approach developed here is to build a corrected surrogate solver through a multi- step process: 1) Sampled simulation results are used to develop a surrogate computational solver that maintains the overall conservative principles of the unmodified governing equations, 2) the surrogate solver is applied to candidate linear and non-linear corrector terms to develop corrections that are consistent with the original conservative principles, 3) constant multipliers on the these terms are calibrated using the experimental observations, and 4) the resulting surrogate solver is used to predict application response for the quantity of interest. This approach and several other calibration-based approaches were applied to an example problem based on the diffusive Burgers' equation. While all the approaches provided some model correction when the measure/calibration quantity was the same as that for an application, only the present approach was able to adequately correct the CompSim results when the prediction quantity was different from the calibration quantity.
97 MATHEMATICS AND COMPUTING↗
Reparameterizing Litter Decomposition Using a Simplified Monte Carlo Method Improves Litter Decay Simulated by a Microbial Model and Alters Bioenergy Soil Carbon Estimates
Litter decomposition determines soil organic matter (SOM) formation and plant-available nutrient cycles. Therefore, accurate model representation of litter decomposition is critical to improving soil carbon (C) projections of bioenergy feedstocks. Soil C models that simulate microbial physiology (i.e., microbial models) are new to bioenergy agriculture, and their parameterization is often based on small datasets or manual calibration to reach benchmarks. Here, we reparameterized litter decomposition in a microbial soil C model (CORPSE - Carbon, Organisms, Rhizosphere, and Protection in the Soil Environment) using the continental-scale Long-term Inter-site Decomposition Experiment Team (LIDET) dataset which documents decomposition across a range of litter qualities over a decade. Here, we conducted a simplified Monte Carlo simulation that constrained parameter values to reduce computational costs. The LIDET-derived parameters improved modeled C and nitrogen (N) remaining, decomposition rates, and litter mean residence times as compared to Baseline parameters. We applied the LIDET litter decomposition parameters to a microbial bioenergy model (Fixation and Uptake of Nitrogen – Bioenergy Carbon, Rhizosphere, Organisms, and Protection) to examine soil C estimates generated by Baseline and LIDET parameters. LIDET parameters increased estimated soil C in bioenergy feedstocks, with even greater increases under elevated plant inputs (i.e., by increasing residue, N fertilization). This was due to the integrated effects of plant litter quantity, quality, and agricultural practices (tillage, fertilization). Collectively, we developed a simple framework for using large-scale datasets to inform the parameterization of microbial models that impacts projections of soil C for bioenergy feedstocks.
54 ENVIRONMENTAL SCIENCES↗
Machine Learning Augmented Predictive and Generative Model for Rupture Life in Ferritic and Austenitic Steels
The Larson-Miller parameter (LMP) offers an efficient and fast scheme to estimate the creep rupture life of alloy materials for high temperature applications. However, owing to poor generalizability and dependence on the constant C, which is typically not known a-priori, estimations using the Larson-Miller parameter often result in suboptimal performance for a wide range of materials. At best it is useful in comparing alloys of similar composition. In this work, three machine learning (ML) schemes were developed for rupture life prediction for 9-12% Cr ferritic-martensitic steels and austenitic stainless steels, i.e., a hierarchical model to parameterize LMP using the LMP constant C to compute rupture life, a hierarchical model to parameterize both C and LMP to compute rupture life, and a direct prediction of rupture life. Specifically, we show that the third scheme, using a gradient boosting algorithm, can be used to train ML models for very accurate prediction of rupture life in a variety of alloys (Pear-son Correlation Coefficient > 0.9 for 9-12% Cr and > 0.8 for austenitic stainless steels). In addition, the Shapley value was used to quantify feature importance, making the model interpretable by identifying the effect of various features on the model performance. Furthermore, a variational autoencoder-based generative model was built by conditioning on the experimental dataset to sample hypothetical synthetic candidate alloys from the learnt joint distribution not existing in both 9-12 % Cr ferritic-martensitic steel and austenitic stainless steel datasets. Finally, based on the predictive and generative model, a reinforcement learning strategy has been proposed to guide experimentalists into designing better heat resistant alloys.
Mamun, Md Osman G.↗
A Test of the Tropical 200- to 300-hPa Warming Rate in Climate Models
Overall climate sensitivity to CO 2 doubling in a general circulation model results from a complex system of parameterizations in combination with the underlying model structure. We refer to this as the model’s “major hypothesis” and we assume it to be testable. We explain four criteria a valid test should meet: measurability, specificity, independence and uniqueness. We argue that temperature change in the tropical 200-300 hPa layer meets these criteria. Comparing modeled to observed trends over the past 60 years using a persistence-robust variance estimator shows that all models warm more rapidly than observations and in the majority of individual cases the discrepancy is statistically significant. We argue that this provides informative evidence against the major hypothesis in most current climate models.
54 ENVIRONMENTAL SCIENCES↗
An observational radiative constraint on hydrologic cycle intensification
We report that intensification of the hydrologic cycle is a key dimension of climate change, with substantial impacts on human and natural systems. A basic measure of hydrologic cycle intensification is the increase in global-mean precipitation per unit surface warming, which varies by a factor of three in current-generation climate models (about 1–3 per cent per kelvin). Part of the uncertainty may originate from atmosphere–radiation interactions. As the climate warms, increases in shortwave absorption from atmospheric moistening will suppress the precipitation increase. This occurs through a reduction of the latent heating increase required to maintain a balanced atmospheric energy budget. Using an ensemble of climate models, here we show that such models tend to underestimate the sensitivity of solar absorption to variations in atmospheric water vapour, leading to an underestimation in the shortwave absorption increase and an overestimation in the precipitation increase. This sensitivity also varies considerably among models due to differences in radiative transfer parameterizations, explaining a substantial portion of model spread in the precipitation response. Consequently, attaining accurate shortwave absorption responses through improvements to the radiative transfer schemes could reduce the spread in the predicted global precipitation increase per degree warming for the end of the twenty-first century by about 35 per cent, and reduce the estimated ensemble-mean increase in this quantity by almost 40 per cent.
58 GEOSCIENCES↗
Fast All-Sky Radiation Model for Solar Applications (FARMS): A Brief Overview of Mechanisms, Performance, and Applications: Preprint
Solar radiation can be computed using radiative transfer models, such as the Rapid Radiation Transfer Model (RRTM) and its general circulation model applications, and used for various energy applications. Due to the complexity of computing radiation fields in aerosol and cloudy atmospheres, simulating solar radiation can be extremely time-consuming, but many approximations--e.g., the two-stream approach and the delta-M truncation scheme--can be utilized. To provide a new fast option for computing solar radiation, we developed the Fast All-sky Radiation Model for Solar applications (FARMS) by parameterizing the simulated diffuse horizontal irradiance and direct normal irradiance for cloudy conditions from the RRTM runs using a 16-stream discrete ordinates radiative transfer method. The solar irradiance at the surface was simulated by combining the cloud irradiance parameterizations with a fast clear-sky model, REST2. To understand the accuracy and efficiency of the newly developed fast model, we analyzed FARMS runs using cloud optical and microphysical properties retrieved using GOES data from 2009-2012. The global horizontal irradiance for cloudy conditions was simulated using FARMS and RRTM for global circulation modeling with a two-stream approximation and compared to measurements taken from the U.S. Department of Energy's Atmospheric Radiation Measurement Climate Research Facility Southern Great Plains site. Our results indicate that the accuracy of FARMS is comparable to or better than the two-stream approach; however, FARMS is approximately 400 times more efficient because it does not explicitly solve the radiative transfer equation for each individual cloud condition. Radiative transfer model runs are computationally expensive, but this model is promising for broad applications in solar resource assessment and forecasting. It is currently being used in the National Solar Radiation Database, which is publicly available from the National Renewable Energy Laboratory at http://nsrdb.nrel.gov.
14 SOLAR ENERGY↗
Final Report for Project: Impacts of stratification and non-equilibrium winds and waves on hub-height winds
This project used a combination of turbulence-resolving large-eddy simulations, single-column modeling (where turbulence is parameterized), and currently available observations to improve, assess, and develop a parameterization of the impact of non-equilibrium wave states and stratification on the buoy-observed winds to establish reliable wind data at the turbine hub-height level. Analysis of turbulence-resolving simulations and observations illuminates the non-linear coupling between the atmosphere and the undulating sea surface. This analysis guides modification of existing boundary layer parameterizations to include wave influences for upward extrapolation of surface-based observations through the turbine layer. Our surface roughness modifications account for the interaction between stratification and the effects of swell’s amplitude and wavelength as well as swell’s relative motion with respect to the mean wind direction. The single-column version of the open source Weather and Research Forecasting (WRF) model (Skamarock et al., 2008) serves as our platform to test our proposed planetary boundary layer parameterization modifications that account for wave effects on marine atmospheric boundary layer flows. WRF has been widely adopted for wind resource analysis and forecasting. The single column version is particularly suitable to development, analysis, and testing of new boundary layer parameterizations. We utilize WRF’s single-column version to verify and validate our proposed modifications to the Mellor-Yamada-Nakanishi-Niino (MYNN) boundary layer parameterization (Nakanishi and Niino, 2004). We explore the implications of our modifications for two-way coupling between WRF and wave models (e.g.,Wavewatch III). The newly implemented parameterization accounting for marine atmospheric boundary layer-wave coupling is then tested in three-dimensional WRF simulations at grid sizes near 1 km. These simulations identify the behavior of simulated winds at the wind plant scale. Overall project conclusions include; In the presence of fast-moving swell (significant wave height Hs = 6.4 m, and phase speed cp = 18 ms -1 ), the atmospheric boundary layer grows more rapidly when waves propagate opposite to the winds compared to when winds and waves are aligned. Pressure drag increases by nearly a factor of 2 relative to the turbulent stress for the extreme case where waves propagate at 180° compared to the pressure gradient forcing. Net wind speed reduces by nearly 15% at hub-height for the 180°-case compared to the 0°-case, and turbulence intensities increase by nearly a factor of 2. These impacts diminish with decreasing wave age; Stratification increases hub height wind speeds and increases the vertical shear of the mean wind across the rotor plane. Fortuitously, this stability-induced enhanced shear does not influence turbulence intensity at hub height, but does increase (decrease) turbulence intensity below (above) hub height. Increased stability also increases the wave-induced pressure stress by ~ 10%; Off the East Coast of the United States during Coupled Boundary Layers Air-Sea Transfer - Low Wind (CBLAST-Low), cases with short fetch include thin stable boundary layers with depths of only a few tens of meters. In the coastal zone, the relationship between the mean wind and the surface fiction velocity (u*(V )) is significantly related to wind direction for weak winds but is not systematically related to the air sea difference of virtual potential temperature, δθv; since waves generally propagate from the south at the Air-Sea Interaction Tower (ASIT) tower, these results suggest that under weak wind conditions waves likely influence surface stress more than stratification does; and Winds and waves are frequently misaligned in the coastal zone. Stability conditions persist for long duration. Over a four year period, the Forschungsplattformen in Nord- und Ostsee Nr. 1 (FINO1) tower (a site with long fetch) primarily experienced weakly-unstable conditions, while stability at the ASIT tower (with a larger influence of offshore winds) experiences a mix of both unstable and stable conditions, where the summer months are predominantly stable. Wind-wave misalignment likely explains the large scatter in observed non-dimensional surface roughness under swell-dominated conditions. Andreas et al.’s (2012) relationship between u* and the 10-m wind speed under predicts the increased u* produced by wave-induced pressure drag produced by misaligned winds and waves. Incorporating wave-state (speed and direction) influences in parameterizations improves predictive skill. In a broad sense, these results suggest that one needs information on winds, temperature, and wave state to upscale buoy measurements to hub-height and across the rotor plane. Our parameterization of wave-state influences on surface drag has been submitted for inclusion in the next publicly available release. In combination, our project elucidates the impacts of two important physical processes (non-equilibrium wind/waves and stratification) on the atmosphere within which offshore turbines operate. This knowledge should help guide and inform manufacturers making critical decisions surrounding design criteria of future turbines to be deployed in the coastal zone. Reductions in annually averaged hub height wind speed error using our new wave-state-aware surface layer parameterization are relatively modest. However since wind turbine power production depends on the wind speed cubed, the error in estimated power production is close to 5%; which is significant and can substantially impact wind resource assessment and decision making with regards to the viability of particular location for a wind plant location. For a single 30-hour forecast, significant reductions in wind speed prediction errors can yield substantially improved wind power forecast skill, thereby mitigating costs and/or increasing revenue through improved; forecasting for maintenance operations and planning; day-ahead forecasting for power trading and resource allocation; and short-term forecasting for dispatch and grid balancing.
17 WIND ENERGY↗
Can machine learning improve the model representation of turbulent kinetic energy dissipation rate in the boundary layer for complex terrain?
Current turbulence parameterizations in numerical weather prediction models at the mesoscale assume a local equilibrium between production and dissipation of turbulence. As this assumption does not hold at fine horizontal resolutions, improved ways to represent turbulent kinetic energy (TKE) dissipation rate (ϵ) are needed. Here, we use a 6-week data set of turbulence measurements from 184 sonic anemometers in complex terrain at the Perdigão field campaign to suggest improved representations of dissipation rate. First, we demonstrate that the widely used Mellor, Yamada, Nakanishi, and Niino (MYNN) parameterization of TKE dissipation rate leads to a large inaccuracy and bias in the representation of ϵ. Next, we assess the potential of machine-learning techniques to predict TKE dissipation rate from a set of atmospheric and terrain-related features. We train and test several machine-learning algorithms using the data at Perdigão, and we find that the models eliminate the bias MYNN currently shows in representing ϵ, while also reducing the average error by up to almost 40 %. Of all the variables included in the algorithms, TKE is the variable responsible for most of the variability of ϵ, and a strong positive correlation exists between the two. These results suggest further consideration of machine-learning techniques to enhance parameterizations of turbulence in numerical weather prediction models.
58 GEOSCIENCES↗
Excess entropy and crystallization in Stillinger-Weber and Lennard-Jones fluids
Molecular dynamics simulations are used to contrast the supercooling and crystallization behaviour of monatomic liquids that exemplify the transition from simple to anomalous, tetrahedral liquids. As examples of simple fluids, we use the Lennard-Jones (LJ) liquid and a pair-dominated Stillinger-Weber liquid (SW{sub 16}). As examples of tetrahedral, water-like fluids, we use the Stillinger-Weber model with variable tetrahedrality parameterized for germanium (SW{sub 20}), silicon (SW{sub 21}), and water (SW{sub 23.15} or mW model). The thermodynamic response functions show clear qualitative differences between simple and water-like liquids. For simple liquids, the compressibility and the heat capacity remain small on isobaric cooling. The tetrahedral liquids in contrast show a very sharp rise in these two response functions as the lower limit of liquid-phase stability is reached. While the thermal expansivity decreases with temperature but never crosses zero in simple liquids, in all three tetrahedral liquids at the studied pressure, there is a temperature of maximum density below which thermal expansivity is negative. In contrast to the thermodynamic response functions, the excess entropy on isobaric cooling does not show qualitatively different features for simple and water-like liquids; however, the slope and curvature of the entropy-temperature plots reflect the heat capacity trends. Two trajectory-based computational estimation methods for the entropy and the heat capacity are compared for possible structural insights into supercooling, with the entropy obtained from thermodynamic integration. The two-phase thermodynamic estimator for the excess entropy proves to be fairly accurate in comparison to the excess entropy values obtained by thermodynamic integration, for all five Lennard-Jones and Stillinger-Weber liquids. The entropy estimator based on the multiparticle correlation expansion that accounts for both pair and triplet correlations, denoted by S{sub trip}, is also studied. S{sub trip} is a good entropy estimator for liquids where pair and triplet correlations are important such as Ge and Si, but loses accuracy for purely pair-dominated liquids, like LJ fluid, or near the crystallization temperature (T{sub thr}). Since local tetrahedral order is compatible with both liquid and crystalline states, the reorganisation of tetrahedral liquids is accompanied by a clear rise in the pair, triplet, and thermodynamic contributions to the heat capacity, resulting in the heat capacity anomaly. In contrast, the pair-dominated liquids show increasing dominance of triplet correlations on approaching crystallization but no sharp rise in either the pair or thermodynamic heat capacities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
REACTIONS FORMING C{sub n=2,10}{sup (0,+)}, C{sub n=2,4}H{sup (0,+)}, AND C{sub 3}H{sub 2}{sup (0,+)} IN THE GAS PHASE: SEMIEMPIRICAL BRANCHING RATIOS
The aim of this paper is to provide a new set of branching ratios (BRs) for interstellar and planetary chemical networks based on a semiempirical model. We applied, instead of zero-order theory (i.e., only the most exoergic decaying channel is considered), a statistical microcanonical model based on the construction of breakdown curves and using experimental high velocity collision BRs for their parameterization. We applied the model to ion-molecule, neutral-neutral, and ion-pair reactions implemented in the few popular databases for astrochemistry, such as KIDA, OSU, and UMIST. We studied the reactions of carbon and hydrocarbon species with electrons, He{sup +}, H{sup +}, CH{sup +}, CH, C, and C{sup +} leading to intermediate complexes of the type C{sub n=2,10}, C{sub n=2,4}H, C{sub 3}H{sub 2}, C{sub n=2,10}{sup +}, C{sub n=2,4}H{sup +}, or C{sub 3}H{sub 2}{sup +}. Comparison of predictions with measurements supports the validity of the model. Huge deviations with respect to database values are often obtained. Effects of the new BRs in time-dependent chemistry for dark clouds and for photodissociation region chemistry with conditions similar to those found in the Horsehead Nebula are discussed.
74 ATOMIC AND MOLECULAR PHYSICS↗
Influences of an entrainment–mixing parameterization on numerical simulations of cumulus and stratocumulus clouds
Abstract. Different entrainment–mixing processes can occur in clouds; however, a homogeneous mixing mechanism is often implicitly assumed in most commonly used microphysics schemes. Here, we first present a new entrainment–mixing parameterization that uses the grid mean relative humidity without requiring the relative humidity of the entrained air. Then, the parameterization is implemented in a microphysics scheme in a large eddy simulation model, and sensitivity experiments are conducted to compare the new parameterization with the default homogeneous entrainment–mixing parameterization. The results indicate that the new entrainment–mixing parameterization has a larger impact on the number concentration, volume mean radius, and cloud optical depth in the stratocumulus case than in the cumulus case. This is because inhomogeneous and homogeneous mixing mechanisms dominate in the stratocumulus and cumulus cases, respectively, which is mainly due to the larger turbulence dissipation rate in the cumulus case. Because stratocumulus clouds break up during the dissipation stage to form cumulus clouds, the effects of this new entrainment–mixing parameterization during the stratocumulus dissipation stage are between those during the stratocumulus mature stage and the cumulus case. A large aerosol concentration can enhance the effects of this new entrainment–mixing parameterization by decreasing the cloud droplet size and evaporation timescale. The results of this new entrainment–mixing parameterization with grid mean relative humidity are validated by the use of a different entrainment–mixing parameterization that uses parameterized entrained air properties. This study sheds new light on the improvement of entrainment–mixing parameterizations in models.
54 ENVIRONMENTAL SCIENCES↗