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

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Propagation of Solar Energetic Particles in Three-dimensional Interplanetary Magnetic Fields: Radial Dependence of Peak Intensities

A functional form I{sub max}(R)=kR{sup −α}, where R is the radial distance of a spacecraft, was usually used to model the radial dependence of peak intensities I{sub max}(R) of solar energetic particles (SEPs). In this work, the five-dimensional Fokker–Planck transport equation incorporating perpendicular diffusion is numerically solved to investigate the radial dependence of SEP peak intensities. We consider two different scenarios for the distribution of a spacecraft fleet: (1) along the radial direction line and (2) along the Parker magnetic field line. We find that the index α in the above expression varies in a wide range, primarily depending on the properties (e.g., location and coverage) of SEP sources and on the longitudinal and latitudinal separations between the sources and the magnetic foot points of the observers. Particularly, whether the magnetic foot point of the observer is located inside or outside the SEP source is a crucial factor determining the values of index α. A two-phase phenomenon is found in the radial dependence of peak intensities. The “position” of the break point (transition point/critical point) is determined by the magnetic connection status of the observers. This finding suggests that a very careful examination of the magnetic connection between the SEP source and each spacecraft should be taken in the observational studies. We obtain a lower limit of R{sup −1.7±0.1} for empirically modeling the radial dependence of SEP peak intensities. Our findings in this work can be used to explain the majority of the previous multispacecraft survey results, and especially to reconcile the different or conflicting empirical values of the index α in the literature.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1982

Experimental investigation of turbulent wall-jets in the presence of adverse pressure gradients in a rectangular diffuser

An experimental study of wall static pressure distributions and mean velocity profiles along a duct and diffuser downstream of wall-jet injection was conducted over a range of diffuser total angles from 15 to 40 deg at injection to core flow mass flux ratios from 0 to 6. Pressure recovery in the diffuser increased with injection ratio and decreased with diffuser total angle. Peak velocities in the wall-jet decayed along the flow and the inner shear layer and outer mixing region grew in thickness along the flow. The inner layer was near similarity condition, but non-similar variations were found in the outer layer. Estimated wall shear stresses depended upon injection mass fluxes, downstream distance and diffuser total angle. Greater decay of peak velocity and larger friction coefficients were found in the diffuser than indicated by correlations from data for a wall-jet without a pressure gradient. At the largest diffuser total angle and the highest injection ratio flow reversal occurred in the core region.

Back, L.↗
DOE OSTI2014

Exploring atmospheres of hot mini-Neptune and extrasolar giant planets orbiting different stars with application to HD 97658b, WASP-12b, CoRoT-2b, XO-1b, and HD 189733b

We calculated an atmospheric grid for hot mini-Neptune and giant exoplanets that links astrophysical observable parameters—orbital distance and stellar type—with the chemical atmospheric species expected. The grid can be applied to current and future observations to characterize exoplanet atmospheres and serves as a reference to interpret atmospheric retrieval analysis results. To build the grid, we developed a one-dimensional code for calculating the atmospheric thermal structure and linked it to a photochemical model that includes disequilibrium chemistry (molecular diffusion, vertical mixing, and photochemistry). We compare the thermal profiles and atmospheric composition of planets at different semimajor axes (0.01 AU ≤ a ≤ 0.1 AU) orbiting F, G, K, and M stars. Temperature and UV flux affect chemical species in the atmosphere. We explore which effects are due to temperature and which are due to stellar characteristics, showing the species most affected in each case. CH{sub 4} and H{sub 2}O are the most sensitive to UV flux, H displaces H{sub 2} as the most abundant gas in the upper atmosphere for planets receiving a high UV flux. CH{sub 4} is more abundant for cooler planets. We explore vertical mixing, to inform degeneracies on our models and in the resulting spectral observables. For lower pressures, observable species like H{sub 2}O or CO{sub 2} can indicate the efficiency of vertical mixing, with larger mixing ratios for a stronger mixing. By establishing the grid, testing the sensitivity of the results, and comparing our model to published results, our paper provides a tool to estimate what observations could yield. We apply our model to WASP-12b, CoRoT-2b, XO-1b, HD189733b, and HD97658b.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

THE EFFECT OF A DYNAMIC INNER HELIOSHEATH THICKNESS ON COSMIC-RAY MODULATION

The time-dependent modulation of galactic cosmic rays in the heliosphere is studied over different polarity cycles by computing 2.5 GV proton intensities using a two-dimensional, time-dependent modulation model. By incorporating recent theoretical advances in the relevant transport parameters in the model, we showed in previous work that this approach gave realistic computed intensities over a solar cycle. New in this work is that a time dependence of the solar wind termination shock (TS) position is implemented in our model to study the effect of a dynamic inner heliosheath thickness (the region between the TS and heliopause) on the solar modulation of galactic cosmic rays. The study reveals that changes in the inner heliosheath thickness, arising from a time-dependent shock position, does affect cosmic-ray intensities everywhere in the heliosphere over a solar cycle, with the smallest effect in the innermost heliosphere. A time-dependent TS position causes a phase difference between the solar activity periods and the corresponding intensity periods. The maximum intensities in response to a solar minimum activity period are found to be dependent on the time-dependent TS profile. It is found that changing the width of the inner heliosheath with time over a solar cycle can shift the time of when the maximum or minimum cosmic-ray intensities occur at various distances throughout the heliosphere, but more significantly in the outer heliosphere. The time-dependent extent of the inner heliosheath, as affected by solar activity conditions, is thus an additional time-dependent factor to be considered in the long-term modulation of cosmic rays.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

X-Ray Studies of the Extended TeV Gamma-Ray Source VER J2019+368

This article reports the results of X-ray studies of the extended TeV γ-ray source VER J2019+368. Suzaku observations conducted to examine properties of the X-ray pulsar wind nebula (PWN) around PSR J2021+3651 revealed that the western region of the X-ray PWN has a source extent of 15{sup ′}×10{sup ′} with the major axis oriented to that of the TeV emission. The PWN-west spectrum was closely fitted by a power law for absorption at N(H)=(8.2{sub −1.1}{sup +1.3})×10{sup 21} cm{sup −2} and a photon index of Γ=2.05±0.12, with no obvious change in the index within the X-ray PWN. The measured X-ray absorption indicates that the distance to the source is much less than the 10 kpc inferred by radio data. Aside from the PWN, no extended emission was observed around PSR J2021+3651 even by Suzaku. Archival data from the XMM-Newton were also analyzed to complement the Suzaku observations, indicating that the eastern region of the X-ray PWN has a similar spectrum (N(H)=(7.5±0.9)×10{sup 21} cm{sup −2} and Γ=2.03±0.10) and source extent up to at least 12{sup ′} along the major axis. The lack of significant change in the photon index and the source extent in X-ray are used to constrain the advection velocity or the diffusion coefficient for accelerated X-ray-producing electrons. A mean magnetic field of ∼3 μG is required to account for the measured X-ray spectrum and reported TeV γ-ray spectrum. A model calculation of synchrotron radiation and inverse Compton scattering was able to explain ∼80% of the reported TeV flux, indicating that the X-ray PWN is a major contributor of VER J2019+368.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Measurements and modeling of the impact of weak magnetic fields on the plasma properties of a planar slot antenna driven plasma source

The radial line slot antenna plasma source is a type of surface wave plasma source driven by a planar slot antenna. Microwave power is transmitted through a slot antenna structure and dielectric window to a plasma characterized by a generation zone adjacent to the window and a diffusion zone that contacts a substrate. The diffusion zone is characterized by a very low electron temperature. This renders the source useful for soft etch applications and thin film deposition processes requiring low ion energy. Another property of the diffusion zone is that the plasma density tends to decrease from the axis to the walls under the action of ambipolar diffusion at distances far from where the plasma is generated. A previous simulation study [Yoshikawa and. Ventzek, J. Vac. Sci. Technol. A 31, 031306 (2013)] predicted that the anisotropy in transport parameters due to weak static magnetic fields less than 50 G could be leveraged to manipulate the plasma profile in the radial direction. These simulations motivated experimental tests in which weak magnetic fields were applied to a radial line slot antenna source. Plasma absorption probe measurements of electron density and etch rate showed that the magnetic fields remote from the wafer were able to manipulate both parameters. A summary of these results is presented in this paper. Argon plasma simulation trends are compared with experimental plasma and etch rate measurements. A test of the impact of magnetic fields on charge up damage showed no perceptible negative effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Droplet Imbibition Enables Nonequilibrium Interfacial Reactions in Charged Microdroplets

A droplet imbibition experiment is proposed to study interfacial effects, which appears to be the main factor influencing reaction acceleration in charged microdroplets produced by electrospray ionization (ESI). One reagent is deposited onto the surface of rapidly moving microdroplets containing the second reagent to be reacted. In this manner, reactions are hindered from reaching equilibrium and monitored in real time by mass spectrometry. We demonstrated this phenomenon using Katritzky chemistry, which is known to proceed either by the solvent-stabilized 2H-pyran intermediate or via the surface-active pseudobase intermediate. Additionally, comparisons with reactions performed using ESI show obvious surface effects in favor of the droplet imbibition experiment. By keeping reactant mole ratio constant, it was demonstrated that similar interfacial effects observed in the droplet imbibition experiment can be reached by allowing ESI microdroplets containing premixed reagents to traverse a distance >16 mm. At such spray distance, molecular diffusion and droplet lifetime become comparable allowing reactants to be enriched at droplet surface. Reactions were also conducted in rapid mixing, theta capillary-based droplets, which showed markedly reduced yields compared with the interfacial droplet imbibition experiment.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Task I: Dark Matter Search Experiments with Cryogenic Detectors: CDMS-I and CDMS-II Task II: Experimental Study of Neutrino Properties: EXO and KamLAND

Dark Matter Search - During the period of performance, our group continued the search for dark matter in the form of weakly interacting massive particles or WIMPs. As a key member of the CDMS (Cryogenic Dark Matter Search) collaboration, we completed the CDMS II experiment which led the field in sensitivity for more than five years. We fabricated all detectors, and participated in detector testing and verification. In addition, we participated in the construction and operation of the facility at the Soudan Underground Laboratory and played key roles in the data acquisition and analysis. Towards the end of the performance period, we began operating the SuperCDMS Soudan experiment, which consists of 15 advanced Ge (9 kg) detectors. The advanced detector design called iZIP grew out of our earlier DOE Particle Detector R&D program which demonstrated the rejection of surface electrons to levels where they are no longer the dominant source of background. Our group invented this advanced design and these larger detectors were fabricated on the Stanford campus in collaboration with the SLAC CDMS group and the Santa Clara University group. The sensitivity reach is expected to be up to 5 times better than CDMS II after two years of operation. We will check the new limits on WIMPs set by XENON100, and we expect improved sensitivity for light mass WIMPs beyond that of any other existing experiment. Our group includes the Spokesperson for SuperCDMS and continues to make important contributions to improvements in the detector technology which are enabling the very low trigger thresholds used to explore the low mass WIMP region. We are making detailed measurements of the charge transport and trapping within Ge crystals, measuring the diffusive trapping distance of the quasiparticle excitations within the Al phonon collector fins on the detector surface, and we are contributing to the development of much improved detector Monte Carlos which are essential to guide the detector design and optimize the analysis. Neutrino Physics – In the period of performance the neutrino group successfully completed the construction of EXO-200 and commissioned the detector. Science data taking started on Jun 1, 2011. With the discovery of the 2-neutrino double-beta decay in 136-Xe and the first measurement of the 0-neutrino mode resulting in the most stringent limit of Majorana masses, our group continues to be a leading innovator in the field of neutrino physics which is central to DOE-HEP Intensity Frontier program. The phenomenon of neutrino oscillations, in part elucidated by our earlier efforts with the Palo Verde and KamLAND experiments, provides the crucial information that neutrino masses are non-zero and, yet, it contains no information on the value of the neutrino mass scale. In recent times our group has therefore shifted its focus to a high sensitivity 0-neutrino double beta decay program, EXO. The 0-neutrino double beta decay provides the best chance of extending the sensitivity to the neutrino mass scale below 10 meV but, maybe more importantly, it tests the nature of the neutrino wave function, providing the most sensitive probe for Majorana particles and lepton number violation. The EXO program, formulated by our group several years ago, plans to use up to tonnes of the isotope 136-Xe to study the 0-neutrino double beta decay mode. The EXO-200 detector is the first step in this program and it represents the only large US-led and based experiment taking data. The EXO-200 isotope enrichment program broke new grounds for the enterprise of double beta decay. The detector design and material selection program paid off, resulting in a background that is among the very best in the field. The “first light" of EXO-200 was very exciting with the discovery -in the first month of data- of the rarest 2-neutrino double beta decay mode ever observed. The lower limit on the 0-neutrino double beta decay half-life, published in Phys. Rev. Lett. and based on the first 120 days of data is the second best but, when translated into a Majorana mass scale, it is one of the most stringent constraint we have on neutrino masses. Indeed, such a limit was the first result to contradict a claim of discovery in 76-Ge for most nuclear matrix elements calculations. As we continue data taking and plan some modest upgrades to EXO-200 our group is also very active in the design of nEXO, a 5 tonne detector based on the technology demonstrated by EXO-200. Over the years we have made it a tradition to explore the frontier and not to be shy about looking in new directions and re-inventing ourselves to best take advantage of the precious few opportunities provided by Nature. We have also cultivated a number of young people at all levels and, by now, many of the undergraduates, graduate students and postdocs educated by this group have leading positions in academia and industry around the world.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1978

Effects of particle drift on cosmic ray transport. II - Analytical solution to the modulation problem with no latitudinal diffusion

An analytical solution to a model of the modulation of galactic cosmic rays in the presence of particle drifts is presented and discussed. The solution assumes an energy-independent radial diffusion coefficient proportional to distance and no latitudinal diffusion, and includes energy-independent particle drift velocities similar to those expected in a Parker spiral magnetic field with an equatorial current sheet. The solutions clearly demonstrate the large effects of drifts on the modulated cosmic-ray intensity. For values of the radial diffusion coefficient and particle drift velocity which are plausible for 1-GV-rigidity protons, the logarithmic radial gradient in the inner solar system is reduced by more than a factor of 5 over the value calculated in the absence of drifts. It is found that even for much smaller values of particle drift velocity and radial diffusion coefficient, such as might be expected for protons with energies of the order of 10 MeV, the effects of the drifts can be substantial.

Isenberg, P. A.↗
NASA NTRS1992

Flow visualizations of perpendicular blade vortex interactions

Helium bubble flow visualizations have been performed to study perpendicular interaction of a turbulent trailing vortex and a rectangular wing in the Virginia Tech Stability Tunnel. Many combinations of vortex strength, vortex-blade separation (Z(sub s)) and blade angle of attack were studied. Photographs of representative cases are presented. A range of phenomena were observed. For Z(sub s) greater than a few percent chord the vortex is deflected as it passes the blade under the influence of the local streamline curvature and its image in the blade. Initially the interaction appears to have no influence on the core. Downstream, however, the vortex core begins to diffuse and grow, presumably as a consequence of its interaction with the blade wake. The magnitude of these effects increases with reduction in Z(sub s). For Z(sub s) near zero the form of the interaction changes and becomes dependent on the vortex strength. For lower strengths the vortex appears to split into two filaments on the leading edge of the blade, one passing on the pressure and one passing on the suction side. At higher strengths the vortex bursts in the vicinity of the leading edge. In either case the core of its remnants then rapidly diffuse with distance downstream. Increase in Reynolds number did not qualitatively affect the flow apart from decreasing the amplitude of the small low-frequency wandering motions of the vortex. Changes in wing tip geometry and boundary layer trip had very little effect.

Rife, Michael C.↗
DOE OSTI2024

Interpenetrating 3D Electrodes for High-Rate Alkaline Water Splitting

Mass transfer is critical for the reaction kinetics and efficiency of alkaline water splitting (AWS). For AWS to operate at high current densities (hundreds of mA/cm 2 ), the device architecture must ensure a large catalytic surface area, rapid ion diffusion, and minimal solution and charge transfer resistances. Effective electrodes should also facilitate gas bubble detachment and release. 3D-printed electrodes have shown promise, but stacking them increases the ion diffusion length and solution resistance. Here we demonstrate a new device architecture with interpenetrating gyroid electrodes, providing a large ion-accessible surface area and gas diffusion channels. This design significantly reduces the interelectrode distance, lowering ion diffusion length and solution resistance. Simulations show faster ion diffusion and higher current density in the interpenetrating configuration compared with separate electrodes. This improved performance, especially at low temperatures and high current densities, highlights a promising strategy for enhancing AWS and other electrochemical systems limited by slow ion diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Theory of exciton transfer and diffusion in conjugated polymers

We describe a theory of Förster-type exciton transfer between conjugated polymers. The theory is built on three assumptions. First, we assume that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, and described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω < J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. The resulting expression for the exciton transfer rate has a familiar form, being a function of the exciton transfer integral and the effective Franck-Condon factors. The effective Franck-Condon factors are functions of the effective Huang-Rhys parameters, which are inversely proportional to the chromophore size. The Born-Oppenheimer expressions were checked against DMRG calculations, and are found to be within 10% of the exact value for a tiny fraction of the computational cost. This theory of exciton transfer is then applied to model exciton migration in conformationally disordered poly(p-phenylene vinylene). Key to this modeling is the assumption that the donor and acceptor chromophores are defined by local exciton ground states (LEGSs). Since LEGSs are readily determined by the exciton center-of-mass wavefunction, this theory provides a quantitative link between polymer conformation and exciton migration. Our Monte Carlo simulations indicate that the exciton diffusion length depends weakly on the conformation of the polymer, with the diffusion length increasing slightly as the chromophores became straighter and longer. This is largely a geometrical effect: longer and straighter chromophores extend over larger distances. The calculated diffusion lengths of ∼10 nm are in good agreement with experiment. The spectral properties of the migrating excitons are also investigated. The emission intensity ratio of the 0-0 and 0-1 vibronic peaks is related to the effective Huang-Rhys parameter of the emitting state, which in turn is related to the chromophore size. The intensity ratios calculated from the effective Huang-Rhys parameters are in agreement with experimental spectra, and the time-resolved trend for the intensity ratio to decrease with time was also reproduced as the excitation migrates to shorter, lower energy chromophores as a function of time. In addition, the energy of the exciton state shows a logarithmic decrease with time, in agreement with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Dynamical evolution of the Oort cometary cloud

The dynamical evolution of comets in the Oort cloud under the influence of stellar perturbations has been modeled using Monte Carlo techniques. It is shown that the cloud has been depleted over the history of the solar system. Comets are lost from the cloud by direct ejection due to close stellar encounters, diffusion of aphelia to distances beyond the sun's sphere of influence, or diffusion of perihelia into the planetary region where Jupiter and Saturn perturbations either eject them on hyperbolic trajectories or capture them to short-period orbits. The population of the cloud is estimated to be 1.0 - 1.5 x 10 to the 12th comets and the total mass is on the order of 1.9 earth masses. In addition to random passing stars, less frequent encounters with giant molecular clouds may play a significant role in randomizing the orbits of comets in the cloud and reducing the effective radius of the sun's sphere of influence.

Weissman, P. R.↗
NASA NTRS1989

Refractory solids in chondrites and comets: How similar

The grains of ice, dust, and organic material that came together to form the solar system have been preserved to differing degrees in the most primitive solar system bodies, asteroids and comets. The study of samples of asteroids (in the form of chondritic meteorites) reveals that the dust component was extensively altered by high-temperature events and processes in the early solar system, before it was aggregated into chondritic planetesimals. The nature of these high-temperature events and processes is not known, but the evidence of their operation is pervasive and unequivocal. Are the refractory particles in comets likely to be similar to these chondrite components. Probably not (except for the presolar carbonaceous grains in chondrites), because the chondritic components are products of severe thermal processing, and all imaginable energy sources that could have provided the heat tend to diminish with distance from the sun. Every indication is that comets formed at much greater radial distances than asteroids, so the particles they incorporated would have experienced less heating. The possibilities cannot be completely ruled out that comets, too, formed inside the present orbit of Jupiter, or that thermally-processed grains were able to diffuse great radial distances before being incorporated in accreting objects, but it is far more likely that most of the refractory grains in comets have been spared the extreme thermal processing that shaped the character of chondritic components.

Wood, John A.↗
DOE OSTI2014

An exact and efficient first passage time algorithm for reaction–diffusion processes on a 2D-lattice

We present an exact and efficient algorithm for reaction–diffusion–nucleation processes on a 2D-lattice. The algorithm makes use of first passage time (FPT) to replace the computationally intensive simulation of diffusion hops in KMC by larger jumps when particles are far away from step-edges or other particles. Our approach computes exact probability distributions of jump times and target locations in a closed-form formula, based on the eigenvectors and eigenvalues of the corresponding 1D transition matrix, maintaining atomic-scale resolution of resulting shapes of deposit islands. We have applied our method to three different test cases of electrodeposition: pure diffusional aggregation for large ranges of diffusivity rates and for simulation domain sizes of up to 4096×4096 sites, the effect of diffusivity on island shapes and sizes in combination with a KMC edge diffusion, and the calculation of an exclusion zone in front of a step-edge, confirming statistical equivalence to standard KMC simulations. The algorithm achieves significant speedup compared to standard KMC for cases where particles diffuse over long distances before nucleating with other particles or being captured by larger islands.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1983

An EBIC equation for solar cells

When an electron beam of a scanning electron microscope (SEM) impinges on an N-P junction, the generation of electron-hole pairs by impact ionization causes a characteristic short circuit current I(sc) to flow. The I(sc), i.e., EBIC (electron beam induced current) depends strongly on the configuration used to investigate the cell's response. In this paper the case where the plane of the junction is perpendicular to the surface is considered. An EBIC equation amenable to numerical computations is derived as a function of cell thickness, source depth, surface recombination velocity, diffusion length, and distance of the junction to the beam-cell interaction point for a cell with an ohmic contact at its back surface. It is shown that the EBIC equation presented here is more general and easier to use than those previously reported. The effects of source depth, ohmic contact, and diffusion length on the normalized EBIC characteristic are discussed.

Luke, K. L.↗
NASA NTRS1980

Performance prediction of straight two dimensional diffusers

A method, based on full viscous calculations, is presented to predict performance of straight two dimensional diffusers. The method predicts adequately the experimental pressure recovery data, up to the point of maximum pressure recovery, for small and large inlet boundary layer thicknesses. It is shown that at the point of maximum pressure recovery the streamwise velocity in the very near wall region varies as Z to the 0.22 power, where Z is the distance from the diffuser wall.

Greywall, M. S.↗
DOE OSTI2020

Effects of pore size on water dynamics in mesoporous silica

Water confined in mesoporous silica plays a central role in its many uses ranging from gas sorption to nanoconfined chemical reactions. Here in this paper, the influence of pore diameter (2.5–5.4 nm) on water hydrogen bond (H-bond) dynamics in MCM41 and SBA15 mesoporous silicas is investigated using femtosecond infrared vibrational spectroscopy and molecular dynamics simulations on selenocyanate (SeCN-) anions dissolved in the pores. As shown recently, SeCN- spectral diffusion is a reliable probe of surrounding water H-bond structural motions. Additionally, the long CN stretch vibrational lifetime facilitates measurement of the full range of confined dynamics, which are much slower than in bulk water. The simulations shed light on quantitative details that are inaccessible from the spatially averaged observables. The dependence of SeCN- orientational relaxation and that of spectral diffusion on the distance from the silica interface are quantitatively described with an exponential decay and a smoothed step-function, respectively. The distance-dependence of both quantities is found to be independent of the diameter of the pores, and the spatial distribution of SeCN- is markedly non-uniform, reaching a maximum between the interface and the pore center. The results indicate that the commonly invoked two-state, or core–shell, model is a more appropriate description of spectral diffusion. Using these insights, we model the full time-dependence of the measured dynamics for all pore sizes and extract the “core” and “shell” dynamical correlation functions and SeCN- spatial probability distributions. The results are critically compared to those for water confined in reverse micelles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗