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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Pretest Modeling A Spent Nuclear Fuel Seismic Shake Test

The U.S. Department of Energy Spent Fuel and Waste Science and Technology (SFWST) program is planning to conduct a series of full-scale shake table tests to simulate hypothetical earthquake conditions and record the response of surrogate spent nuclear fuel (SNF) assemblies in a dry canister storage system mockup. The shake table motions will represent a range of hypothetical earthquake conditions at hypothetical locations in the continental U.S. to generally define the range of mechanical loads that SNF can be expected to experience during extended dry storage periods. This paper describes the pretest predictions made with LS-DYNA models of the mockup storage systems. The test will use two dry storage system configurations, a mockup vertical concrete cask (VCC) and a mockup horizontal storage module (HSM). The test will use a production-quality canister and basket. Within the canister will be four instrumented fuel assemblies with fuel rods containing surrogate mass and 28 instrumented dummy assemblies that are intended to match the mass and outer dimension of a fuel assembly. The finite element models include models of the VCC and HSM on the shake table to calculate the system level dynamic responses and separate single fuel assembly models to calculate stress and strain in fuel assembly components. Both types of models include nonlinear behavior like rod-to-rod contact and the ability for VCC’s to rock and slide. This paper presents the expected response of the VCC, HSM, and fuel assemblies to the shake table testing that is planned to start in April of 2024. The earthquake conditions represent seismic hazards in the 2,000-to-20,000-year return period range. The test data is expected to confirm the expectation that fuel rod cladding will remain intact, fuel assembly structural components like guide tubes will remain intact, and no significant VCC sliding or tipping will occur in the range of conditions to be tested with the shake table.

Klymyshyn, Nicholas A.↗
DOE OSTI2025

Bridging the length scales in ionic separations via data-driving machine learning

We pursued a data science driven machine learning (ML) approach that blended molecular scale attributes informed from molecular dynamics (MD) simulation and materials properties to the selectivity and energy efficiency in targeted ionic separations using electric fields. The model mixtures investigated for ionic separations are pH sensitive and include organic acids, silica and boron, transition metals, such as copper and chromium. There were two major research thrusts of this project. Firstly, we investigated surrogate models and deep learning that relate material chemistries and structures to selective transport of ionic species under applied electric fields. Secondly we investigated how the bipolar junction interfacial design and water dissociation catalyst in bipolar membranes affect reverse bias polarization behavior and pH modulation in deionization platforms as a function of the platform operating parameters (e.g., cell voltage, residence time, and salt feed concentration). As a result of this work, we also were able to start a new direction, namely ML models for molecular design of surfactants.

36 MATERIALS SCIENCE↗
DOE OSTI2025

An Educational Guide for 2D Stellar Structure Calculations of Rapidly Rotating Stars using the ESTER code

The Evolution STEllaire en Rotation (ESTER) code is the first 2D stellar structure code to be made open-source and freely available to the astronomy and astrophysics community. An important and novel advancement of this code is that it can reproduce the distorted shape and observable signatures (e.g., gravity darkening) of rapidly rotating stars. ESTER also calculates the steady-state large-scale flows within the star, namely their differential rotation and associated meridional circulation. In this report, we explore and document the physics implemented within version 1.1.0rc2 of the ESTER code, in a way that complements published descriptions. We illustrate this physics by plotting how stellar structure parameters vary through stellar interiors at a range of latitudes and at different angular velocities. We investigate how the thin convective envelopes of intermediate mass stars vary with latitude when rapidly rotating, becoming deeper and thicker near the equator. Simple comparisons of ESTER model predictions (e.g., central temperature and density, luminosity) with the output from the Modules for Experiments in Stellar Astrophysics (MESA) code [Paxton et al., 2010] shows generally good agreement. Additional comparisons provide important benchmarking and verification for ESTER as a comparatively young code. Finally, we provide a guide for installing and running the code on our local university cluster, aimed at helping students to begin work.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2011

Evaluation of Drogue Parachute Damping Effects Utilizing the Apollo Legacy Parachute Model

Drogue parachute damping is required to dampen the Orion Multi Purpose Crew Vehicle (MPCV) crew module (CM) oscillations prior to deployment of the main parachutes. During the Apollo program, drogue parachute damping was modeled on the premise that the drogue parachute force vector aligns with the resultant velocity of the parachute attach point on the CM. Equivalent Cm(sub q) and Cm(sub alpha) equations for drogue parachute damping resulting from the Apollo legacy parachute damping model premise have recently been developed. The MPCV computer simulations ANTARES and Osiris have implemented high fidelity two-body parachute damping models. However, high-fidelity model-based damping motion predictions do not match the damping observed during wind tunnel and full-scale free-flight oscillatory motion. This paper will present the methodology for comparing and contrasting the Apollo legacy parachute damping model with full-scale free-flight oscillatory motion. The analysis shows an agreement between the Apollo legacy parachute damping model and full-scale free-flight oscillatory motion.

Currin, Kelly M.↗
NASA NTRS2013

Ionospheric Simulation System for Satellite Observations and Global Assimilative Modeling Experiments (ISOGAME)

ISOGAME is designed and developed to assess quantitatively the impact of new observation systems on the capability of imaging and modeling the ionosphere. With ISOGAME, one can perform observation system simulation experiments (OSSEs). A typical OSSE using ISOGAME would involve: (1) simulating various ionospheric conditions on global scales; (2) simulating ionospheric measurements made from a constellation of low-Earth-orbiters (LEOs), particularly Global Navigation Satellite System (GNSS) radio occultation data, and from ground-based global GNSS networks; (3) conducting ionospheric data assimilation experiments with the Global Assimilative Ionospheric Model (GAIM); and (4) analyzing modeling results with visualization tools. ISOGAME can provide quantitative assessment of the accuracy of assimilative modeling with the interested observation system. Other observation systems besides those based on GNSS are also possible to analyze. The system is composed of a suite of software that combines the GAIM, including a 4D first-principles ionospheric model and data assimilation modules, an Internal Reference Ionosphere (IRI) model that has been developed by international ionospheric research communities, observation simulator, visualization software, and orbit design, simulation, and optimization software. The core GAIM model used in ISOGAME is based on the GAIM++ code (written in C++) that includes a new high-fidelity geomagnetic field representation (multi-dipole). New visualization tools and analysis algorithms for the OSSEs are now part of ISOGAME.

Pi, Xiaoqing↗
NASA NTRS1985

The use of satellite data in understanding and predicting convective and large-scale dynamical processes

A two-layer truncated baroclinic spectral model was developed to study the long-term evolution of disturbances to a baroclinically unstable mean flow. Topography and crudely-parameterized radiative processes were accounted for. As a result of Robert Schlaak's discovery of the underlying barotropic nature of the index oscillation as well as reviewers suggestions about the original manuscript, the model has been revised to allow for barotropic as well as baroclinic wave-mean flow interactions. The form-drag exerted by the topography on the barotropic part of the mean flow is larger than on the baroclinic part and thus researchers anticipate significant changes from the original calculations on the index oscillation when it is strongly modulated by topography. Researchers believe that since the index oscillation accounts for a significant portion of atmospheric temporal variance, the long term predictability could be improved if reliable forecasts of the index oscillation were available. Two spectral models of the index oscillation, one barotropic and the other baroclinic, have been developed. The latter allows for moisture, radiation, land-sea temperature countrasts, and energy exchanges with the underlying surface.

Dutton, J. A.↗
DOE OSTI2026

Seasonal variation of the surface cross-shelf exchange in the northern South China Sea: a Lagrangian perspective

Previous studies on cross-shelf exchange, predominantly adopted an Eulerian perspective, struggled to identify water sources and pathways. Using a high-resolution regional ocean modeling system (ROMS) and Lagrangian particle tracking, this study systematically investigates the seasonal variation and dynamics of surface cross-shelf exchange in the northern South China Sea (NSCS) from a Lagrangian perspective. Based on daily released 30-day drifter trajectories we identify the key pathways, source regions for surface cross-shelf exchange, revealing pronounced seasonal variability. Results show the surface cross-shelf exchange generally following monsoon-driven Ekman transport. However, local dynamics, especially topographic modulation, can outweigh the expected Ekman-driven transport, producing surface exchange patterns opposite to that predicted from the prevailing winds. Topographic effects vary across different scales. In the coastal waters of western Guangdong during winter, despite downwelling-favorable winds, the modulation of alongshore currents by island topography induces an eastward pressure gradient. This gradient, through geostrophic balance, drives offshore flows opposite to wind-driven Ekman onshore transport. Furthermore, the eastern widened shelf exhibits a distinct seasonal variation of cross-shelf exchange, with strong offshore transport (opposite to the direction of Ekman transport) in winter and exceedingly weak exchange in summer. Analysis of the underlying mechanisms reveals that this winter offshore transport is primarily attributed to geostrophic flows driven by surface pressure gradient that is jointly modulated by the Kuroshio intrusion and local widened shelf topography, and enhanced by cumulative submesoscale processes. In summer, a persistent and strong along-isobath jet acts as a dynamic barrier, effectively suppressing the exchange. These findings highlight the important role of topography in regulating surface material transport, and have important implications for predicting the advection and dispersion of plankton or oil spills over the continental shelf influenced by monsoon.

Hao, Dongliang↗
DOE OSTI2025

Minimal implicit-solvent coarse-grained simulation of Pluronic block copolymers with ionic liquids

Pluronic block copolymers, composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) in a triblock structure (PEO–PPO–PEO), are well known for their amphiphilic character and ability to self‐assemble into micelles in aqueous solution. The addition of ionic liquids (ILs) can further modulate the core–shell structures of these copolymers, influencing their stability, critical micellization temperature, and size. However, fully atomistic simulations often become prohibitively expensive due to the size and complexity of these systems. In this work, coarse‐grained simulations using a minimal implicit‐solvent model were performed to examine how two classes of ILs, namely, 1‐alkyl‐3‐methylimidazolium ([C n C 1 im]) and 1‐alkyl‐3‐methylpyrrolidinium ([C n C 1 pyrr]), change the micellization of Pluronic block copolymers in aqueous solution. The effects of IL concentration and alkyl group length were investigated, and the model greatly improved the efficiency of simulating large‐scale micelle systems. Furthermore, the numerical simulations are qualitatively compared with experimental investigations. Our results show that adding ILs expands the micelle core by embedding IL tails among the PPO blocks, thereby increasing overall micelle size. Less polar ILs generally induce more pronounced micellar growth. However, the effect of IL tail length on conformation and micellar packing is non‐monotonic. Up to moderate chain lengths (around C8–C10), the IL tails can extend sufficiently to increase local separation within the micelle; at longer tail lengths, enhanced hydrophobic clustering and steric hindrance cause the tails to bend or fold, capping further expansion. In addition, although block copolymer chains tend to pack more closely in the presence of longer‐tailed ILs, the random coil size of an individual polymer chain does not necessarily shrink. Meanwhile, these insights provide a deeper understanding of how Pluronic/IL systems interact, informing applications in drug delivery, cosmetics, food, and environmental engineering. Finally, our minimal implicit‐solvent model can be applied to larger systems and longer timescales, substantially reducing computational cost while reproducing key structural trends observed experimentally.

Atomistic simulations↗
DOE OSTI2020

Hierarchical morphologies in co-sputter deposited thin films

Co-depositions of immiscible alloy films at specific processing conditions have yielded hierarchical microstructures which consist of distinct features at multiple length scales, often agglomerates and concentration modulations on the sub-micrometer-scale and fine nanoprecipitates in a matrix on the nanoscale. The present work examined a series of immiscible alloy systems: Cu-Mo, Cu-Ag, Cu-Fe, Cu-Ta, Mo-Ag, Cu-Mo-Ag, to determine the kinetic conditions favorable for hierarchical organization and the formation mechanism of such structures. Thin films of six immiscible systems were sputter co-deposited over a range of deposition rates from 0.12 to 2 nm/s and various temperatures from 400 to 800°C. The resulting microstructures indicate that hierarchical structures form with sufficient disparity in kinetic energy between the constituent atoms, one species being highly mobile (A) and the other relatively immobile (B). This condition arises typically at elevated deposition temperatures and reduced deposition rates but is also alloy dependent. The hierarchical structures form during deposition via phase separation and self-organization processes across the multiple length scales. The adatoms diffuse on the film surface with the highly mobile species swiftly agglomerating into A-rich domains within which B-rich nanoprecipitates form, often self-organizing into periodic arrays. The smallest B-rich nanoprecipitates in the A-rich domains are found to be coherent and in a metastable crystal structure (B taking the structure of A), but coarser precipitates that exhibit the equilibrium structure of B element. The A-rich domains are surrounded by a B-rich matrix that phase-separates into a concentration modulated structure. In conclusion, the observations are interpreted via a model incorporating material properties and process parameters.

36 MATERIALS SCIENCE↗
NASA NTRS2005

The QBO as Potential Amplifier and Conduit to Lower Altitudes of Solar Cycle Influence

The solar cycle (SC) effect in the lower atmosphere has been linked observationally to the Quasi-biennial Oscillation (QBO), which is generated primarily by small-scale gravity waves. Salby and Callaghan analyzed the QBO observations covering more than 40 years and found that it contains a relatively large SC signature at 20 km. Following up on a 2D study with our Numerical Spectral Model (NSM), we discuss here a 3D study in which we simulated the QBO under the influence of the SC. For a SC period of 10 years, the amplitude of the relative variations of radiative forcing is taken to vary from 0.2% at the surface to 2% at 50 km to 20% at 100 km and above. This model produces in the lower stratosphere a relatively large modulation of the QBO, which appears to be related to the SC and is in qualitative agreement with the observations. Further studies are needed, (1) to determine whether the effect is real and the results are robust and (2) to explore the mechanism(s) that may amplify the SC effect. Quasi-decadal oscillations, generated internally by the QBO interacting with the seasonal cycles, may interfere with or aid the SC effect.

Mayr, Hans G.↗
NASA NTRS2006

Analyzing Electric Field Morphology Through Data-Model Comparisons of the GEM IM/S Assessment Challenge Events

The storm-time inner magnetospheric electric field morphology and dynamics are assessed by comparing numerical modeling results of the plasmasphere and ring current with many in situ and remote sensing data sets. Two magnetic storms are analyzed, April 22,2001 and October 21-23,2001, which are the events selected for the Geospace Environment Modeling (GEM) Inner Magnetosphere/Storms (IM/S) Assessment Challenge (IMSAC). The IMSAC seeks to quantify the accuracy of inner magnetospheric models as well as synthesize our understanding of this region. For each storm, the ring current-atmosphere interaction model (RAM) and the dynamic global core plasma model (DGCPM) were run together with various settings for the large-scale convection electric field and the nightside ionospheric conductance. DGCPM plasmaspheric parameters were compared with IMAGE-EUV plasmapause extractions and LANL-MPA plume locations and velocities. RAM parameters were compared with Dst*, LANL-MPA fluxes and moments, IMAGE-MENA images, and IMAGE-HENA images. Both qualitative and quantitative comparisons were made to determine the electric field morphology that allows the model results to best fit the plasma data at various times during these events. The simulations with self-consistent electric fields were, in general, better than those with prescribed field choices. This indicates that the time-dependent modulation of the inner magnetospheric electric fields by the nightside ionosphere is quite significant for accurate determination of these fields (and their effects). It was determined that a shielded Volland-Stern field description driven by the 3-hour Kp index yields accurate results much of the time, but can be quite inconsistent. The modified Mcllwain field description clearly lagged in overall accuracy compared to the other fields, but matched some data sets (like Dst*) quite well. The rankings between the simulations varied depending on the storm and the individual data sets, indicating that each field description did well for some place, time, and energy range during the events, as well as doing less well in other places, times, and energies. Several unresolved issues regarding the storm-time inner magnetospheric electric field are discussed.

Liemohn, Michael W.↗
NASA NTRS2017

Computational Design and Analysis of a Transonic Natural Laminar Flow Wing for a Wind Tunnel Model

A natural laminar flow (NLF) wind tunnel model has been designed and analyzed for a wind tunnel test in the National Transonic Facility (NTF) at the NASA Langley Research Center. The NLF design method is built into the CDISC design module and uses a Navier-Stokes flow solver, a boundary layer profile solver, and stability analysis and transition prediction software. The NLF design method alters the pressure distribution to support laminar flow on the upper surface of wings with high sweep and flight Reynolds numbers. The method addresses transition due to attachment line contamination/transition, Gortler vortices, and crossflow and Tollmien-Schlichting modal instabilities. The design method is applied to the wing of the Common Research Model (CRM) at transonic flight conditions. Computational analysis predicts significant extents of laminar flow on the wing upper surface, which results in drag savings. A 5.2 percent scale semispan model of the CRM NLF wing will be built and tested in the NTF. This test will aim to validate the NLF design method, as well as characterize the laminar flow testing capabilities in the wind tunnel facility.

Lynde, Michelle N.↗
NASA NTRS2016

The Primordial Inflation Explorer (PIXIE)

The Primordial Inflation Explorer is an Explorer-class mission to open new windows on the early universe through measurements of the polarization and absolute frequency spectrum of the cosmic microwave background. PIXIE will measure the gravitational-wave signature of primordial inflation through its distinctive imprint in linear polarization, and characterize the thermal history of the universe through precision measurements of distortions in the blackbody spectrum. PIXIE uses an innovative optical design to achieve background-limited sensitivity in 400 spectral channels spanning over 7 octaves in frequency from 30 GHz to 6 THz (1 cm to 50 micron wavelength). Multi-moded non-imaging optics feed a polarizing Fourier Transform Spectrometer to produce a set of interference fringes, proportional to the difference spectrum between orthogonal linear polarizations from the two input beams. Multiple levels of symmetry and signal modulation combine to reduce systematic errors to negligible levels. PIXIE will map the full sky in Stokes I, Q, and U parameters with angular resolution 2.6 degrees and sensitivity 70 nK per 1degree square pixel. The principal science goal is the detection and characterization of linear polarization from an inflationary epoch in the early universe, with tensor-to-scalar ratio r < 10(exp. -3) at 5 standard deviations. The PIXIE mission complements anticipated ground-based polarization measurements such as CMBS4, providing a cosmic-variance-limited determination of the large-scale E-mode signal to measure the optical depth, constrain models of reionization, and provide a firm detection of the neutrino mass (the last unknown parameter in the Standard Model of particle physics). In addition, PIXIE will measure the absolute frequency spectrum to characterize deviations from a blackbody with sensitivity 3 orders of magnitude beyond the seminal COBE/FIRAS limits. The sky cannot be black at this level; the expected results will constrain physical processes ranging from inflation to the nature of the first stars and the physical conditions within the interstellar medium of the Galaxy. We describe the PIXIE instrument and mission architecture required to measure the CMB to the limits imposed by astrophysical foregrounds.

Kogut, Alan↗
DOE OSTI2024

Analyzing the impact of design factors on solar module thermomechanical durability using interpretable machine learning techniques

Solar modules in utility-scale systems are expected to maintain decades of lifetime to rival conventional energy sources. However, cyclic thermomechanical loading often degrades their long-term performance, highlighting the importance of effective design to mitigate thermal expansion mismatches between module materials. Given the complex composition of solar modules, isolating the impact of individual components on overall durability remains a challenging task. In this work, we analyze a comprehensive data set that comprises bill-of-materials (BOM) and thermal cycling power loss from 251 distinct module designs to identify the predominant design factors and their impacts on the thermomechanical durability of modules. The methodology of our analysis combines machine learning modeling (random forest) and Shapley additive explanation (SHAP) to correlate design factors with power loss and interpret the model’s decision-making. The interpretation reveals that silicon type (monocrystalline or polycrystalline), encapsulant thickness, busbar numbers, and wafer thickness predominantly influence the degradation. With lower power loss of around 0.6% on average in the SHAP analysis, monocrystalline cells present better durability than polycrystalline cells. This finding is further substantiated by statistical testing on our raw data set. The SHAP analysis also demonstrates that while thicker encapsulants lead to reduced power loss, further increasing their thickness over around 0.6 to 0.7 mm does not yield additional benefits, particularly for the front side one. In addition, other important BOM features such as the number of busbars are analyzed. This study provides a blueprint for utilizing explainable machine learning techniques in a complex material system and can potentially guide future research on optimizing the design of solar modules.

14 SOLAR ENERGY↗
DOE OSTI2022

Sockeye Heat Pipe Analysis Code Verification and Validation

Some of the most promising microreactor designs currently under development utilize heat pipe technology to transfer heat from the reactor core to the secondary side heat exchanger, due to the technology’s compactness, efficiency, passivity, and reliability. Sockeye is an engineering-scale heat pipe tool developed under the Nuclear Energy Advanced Modeling and Simulation Program to be used for the design and safety analysis of microreactors. Sockeye’s core capability lies in a 1D, two-phase, compressible flow model, used to simulate the working fluid inside the heat pipe. Sockeye is built on the Multiphysics Object-Oriented Simulation Environment framework, which allows for seamless multiphysics coupling with other Nuclear Energy Advanced Modeling and Simulation tools and can thus be used in a full-scale simulation of a microreactor assembly, which can include hundreds of heat pipes. This paper presents some initial verification and validation assessments performed for Sockeye. We demonstrate good agreement between Sockeye’s numerical results and steady-state analytic solutions for velocity and pressure drop, with differences attributable to the underlying assumptions made by the analytic solutions. We also show that Sockeye reproduces analytic predictions of key operational limits, such as the capillary limit and the sonic limit. Finally, we compare Sockeye results to experimental data for the SAFE-30 heat pipe module test.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
NASA NTRS2009

Modeling and Simulation of the Second-Generation Orion Crew Module Air Bag Landing System

Air bags were evaluated as the landing attenuation system for earth landing of the Orion Crew Module (CM). Analysis conducted to date shows that airbags are capable of providing a graceful landing of the CM in nominal and off-nominal conditions such as parachute failure, high horizontal winds, and unfavorable vehicle/ground angle combinations, while meeting crew and vehicle safety requirements. The analyses and associated testing presented here surround a second generation of the airbag design developed by ILC Dover, building off of relevant first-generation design, analysis, and testing efforts. In order to fully evaluate the second generation air bag design and correlate the dynamic simulations, a series of drop tests were carried out at NASA Langley s Landing and Impact Research (LandIR) facility in Hampton, Virginia. The tests consisted of a full-scale set of air bags attached to a full-scale test article representing the Orion Crew Module. The techniques used to collect experimental data, develop the simulations, and make comparisons to experimental data are discussed.

Timmers, Richard B.↗
DOE OSTI2025

Numerical case study of the aerosol–cloud interactions in warm boundary layer clouds over the eastern North Atlantic with an interactive chemistry module

The presence of warm boundary layer stratiform clouds over the eastern North Atlantic (ENA) region is commonly influenced by the Azores High, especially during the summer season. To investigate comprehensive aerosol–cloud interactions, this study employs the Weather Research and Forecasting model coupled with a chemistry component (WRF-Chem), incorporating aerosol chemical components that are relevant to the formation of cloud condensation nuclei (CCN) and accounting for aerosol spatiotemporal variation. This study focuses on aerosol indirect effects, particularly the long-range transport of aerosols, in the ENA region under three different weather regimes: a ridge with a surface high-pressure system, a post-trough with a surface high-pressure system, and a weak trough. The WRF-Chem simulations conducted at a near-large-eddy scale offer valuable insights into the model's performance, especially in terms of its ability to use high spatial resolution to capture mesoscale cloud features across various weather regimes. Our result shows that introducing 5 times more aerosols to either non-precipitating or precipitating clouds significantly increases ambient CCN numbers, resulting in, to varying degrees, higher liquid water path (LWP) values. The substantial aerosol–cloud interaction especially occurs in the precipitating clouds and demonstrates the susceptibility of the LWP to changes in CCN under different regimes. Conversely, thin, non-rain clouds at the edges of a cloud system are prone to evaporation, exhibiting an aerosol drying effect. The aerosols released during this process transition back to the accumulation mode, facilitating future activation. This dynamic behavior is not adequately represented in prescribed-aerosol simulations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Integrated Quantum-Classical Protocol for the Realistic Description of Solvated Multinuclear Mixed-Valence Transition-Metal Complexes and Their Solvatochromic Properties

Linear cyanide-bridged polymetallic complexes, which undergo photoinduced metal-to-metal charge transfer, represent prototypical systems for studying long-range electron-transfer reactions and understanding the role played by specific solute–solvent interactions in modulating the excited-state dynamics. Here, to tackle this problem, while achieving a statistically meaningful description of the solvent and of its relaxation, one needs a computational approach capable of handling large polynuclear transition-metal complexes, both in their ground and excited states, as well as the ability to follow their dynamics in several environments up to nanosecond time scales. Here, we present a mixed quantum classical approach, which combines large-scale molecular dynamics (MD) simulations based on an accurate quantum mechanically derived force field (QMD-FF) and self-consistent QMD polarized point charges, with IR and UV–vis spectral calculations to model the solvation dynamics and optical properties of a cyano-bridged trinuclear mixed-valence compound (trans-[(NC) 5 Fe III (μ-CN)Ru II (pyridine) 4 (μ-NC)Fe III (CN) 5 ] 4– ). We demonstrate the reliability of the QMD-FF/MD approach in sampling the solute conformational space and capturing the local solute–solvent interactions by comparing the results with higher-level quantum mechanics/molecular mechanics (QM/MM) MD reference data. The IR spectra calculated along the classical MD trajectories in different solvents correctly predict the red shift of the CN stretching band in the aprotic medium (acetonitrile) and the subtle differences measured in water and methanol, respectively. By explicitly including the solvent molecules around the cyanide ligands and calculating the thermal averaged absorption spectra using time-dependent density functional theory calculations within the Tamm–Dancoff approximation, the experimental solvatochromic shift is quantitatively reproduced going from water to methanol, while it is overestimated for acetonitrile. This discrepancy can likely be traced back to the lack of important dispersion interactions between the solvent cyano groups and the pyridine substituents in our micro solvation model. The proposed protocol is applied to the ground state in water, methanol, and acetonitrile and can be flexibly generalized to study excited-state nonequilibrium solvation dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗