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At least 325 records · Page 18

A comparison of strategies for state-selective coherent Raman excitation

Here we report on the theoretical and experimental evaluation of state-selective bond activation for coherent Raman spectroscopy and control of chemical reactivity. We compare six different strategies for state-selective activation using shaped broadband femtosecond laser pulses. Results for a pair of long pulses with different wavelengths are also considered. For each of these approaches, we report on their theoretical and experimental ability to excite a desired vibrational mode while minimizing excitation of other modes including harmonics. We find that the double parabola spectral phase function gives the most intense Raman excitation with 10 cm -1 selectivity with the lowest background. The sinusoidal phase function produces intense Raman excitation with high selectivity but gives a series of harmonic excitations which could hinder selectivity. Implications of this study on several fields ranging from sensing, to controlling chemical reactions, and selective excited state excitation by X-ray pulses are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancements to the Open Access Spectral Band Adjustment Factor Online Calculation Tool for Visible Channels

With close to 40 years of satellite observations, from which, cloud, land-use, and aerosol parameters can be measured, inter-consistent calibrations are needed to normalize retrievals across satellite records. Various visible-sensor inter-calibration techniques have been developed that utilize radiometrically stable Earth targets, e.g., deep convective clouds and desert/polar ice pseudo-invariant calibration sites. Other equally effective, direct techniques for intercalibration between satellite imagers are simultaneous nadir overpass comparisons and ray-matched radiance pairs. Combining independent calibration results from such varied techniques yields robust calibration coefficients, and is a form of self-validation. One potential source of significant error when cross-calibrating satellite sensors, however, are the often small but substantial spectral discrepancies between comparable bands, which must be accounted for. As such, visible calibration methods rely on a Spectral Band Adjustment Factor (SBAF) to account for the spectral-response function- induced radiance differences between analogous imagers. The SBAF is unique to each calibration method as it is a function of the Earth-reflected spectra. In recent years, NASA Langley pioneered the use of SCIAMACHY-, GOME-2-, and Hyperion-retrieved Earth spectra to compute SBAFs. By carefully selecting hyperspectral footprints that best represent the conditions inherent to an inter-calibration technique, the uncertainty in the SBAF is greatly reduced. NASA Langley initially provided the Global Space-based Inter-calibration System processing and research centers with online SBAF tools, with which users select conditions to best match their calibration criteria. This article highlights expanded SBAF tool capabilities for visible wavelengths, with emphasis on the use of the spectral range filtering for the purpose of separating scene conditions for the channel that the SBAF is needed based on the reflectance values of other bands. In other words, spectral filtering will enable better scene-type selection for bands where scene determination is difficult without information from other channels, which should prove valuable to users in the calibration community.

Scarino, Benjamin↗

Spectral fluctuations in the Sachdev-Ye-Kitaev model

We present a detailed quantitative analysis of spectral correlations in the Sachdev-Ye-Kitaev (SYK) model. We find that the deviations from universal Random Matrix Theory (RMT) behavior are due to a small number of long-wavelength fluctuations (of the order of the number of Majorana fermions N ) from one realization of the ensemble to the next one. These modes can be parameterized effectively in terms of Q-Hermite orthogonal polynomials, the main contribution being due to scale fluctuations for which we give a simple analytical estimate. Our numerical results for N = 32 show that only the lowest eight polynomials are needed to eliminate the nonuniversal part of the spectral fluctuations. The covariance matrix of the coefficients of this expansion can be obtained analytically from low-order double-trace moments. We evaluate the covariance matrix of the first six moments and find that it agrees with the numerics. We also analyze the spectral correlations in terms of a nonlinear σ-model, which is derived through a Fierz transformation, and evaluate the one and two-point spectral correlation functions to two-loop order. The wide correlator is given by the sum of the universal RMT result and corrections whose lowest-order term corresponds to scale fluctuations. However, the loop expansion of the σ-model results in an ill-behaved expansion of the resolvent, and it gives universal RMT fluctuations not only for q= 4 or higher even q-body interactions, but also for the q= 2 SYK model albeit with a much smaller Thouless energy while the correct result in this case should have been Poisson statistics. In our numerical studies we analyze the number variance and spectral form factor for N = 32 and q = 4. We show that the quadratic deviation of the number variance for large energies appears as a peak for small times in the spectral form factor. After eliminating the long-wavelength fluctuations, we find quantitative agreement with RMT up to an exponentially large number of level spacings for the number variance or exponentially short times in the case of the spectral form factor.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Joint Retrieval of Surface BRDF from Geostationary and Polar-Orbiting Satellite Sensors

The latest geostationary sensors like GOES 16/17 ABI and Himawari 8/9 AHI provide high frequent observations of the Earth surface with continuously changing solar illumination geometries, which allow us to retrieve the surface Bidirectional Reflectance Distribution Function (BRDF) with dedicated atmospheric correction algorithms like MAIAC (Multi-Angle Implementation of Atmospheric Correction). However, because the viewing geometry of a specific location from the geostationary satellites are fixed, the angular sampling of surface BRDF by GEO (Geostationary Earth Orbit) sensors is far from comprehensive. This study tries to address this issue by exploring a GEO-LEO (Low-Earth-Orbit) synergy, in particular, jointly retrieving surface BRDF parameters with concurrent ABI/AHI and VIIRS top-of-atmosphere (TOA) reflectance for the near-infrared (NIR) band. The NIR band is chosen because the ABI, AHI, and VIIRS instruments have very similar spectral response functions in this band and therefore simplifies the requirements for cross-sensor radiometric calibration. We compile ABI/AHI and VIIRS TOA data with the best quality (cloud-free and low aerosol loading) at chosen AERONET sites. We then run the GeoNEX MAIAC algorithm to retrieve the Ross-Thick-Li-Sparse (RTLS) surface BRDF parameters with or without the AEORNET measured atmospheric aerosol optical depth (AOD) as inputs. The joint retrieval results are considered the best estimate of surface BRDF. We compare the joint BRDF retrievals with the corresponding MAIAC BRDF products, retrieved with ABI/AHI or VIIRS separately, to evaluate their differences. We expect that the jointly retrieved BRDF data are more robust than the standard products and may help us reduce uncertainties in higher-level earth observation satellite products.

Remote Sensing↗

Hyperspectral radiance mapping and chromatic correction for temperature measurement in laser-heated diamond anvil cells

In laser-heated diamond anvil cell (DAC) experiments, the effective heated region typically decreases in size with increasing pressure, leading to steeper thermal gradients. Under these conditions, chromatic aberration in the optical path from sample to detector can significantly create bias in spectro-radiometric temperature measurement. We present a radiance-mapping approach using a hyperspectral camera that records 25 spectral channels spanning 605–875 nm at each pixel in a single exposure, providing spatially and spectrally resolved radiance in each frame. This enables chromatic effects to be recorded and corrected in data processing. We developed a procedure for hyperspectral mapping, involving per-camera calibration, crosstalk removal, measured spectral throughput functions, and optional sub-pixel co-registration to minimize chromatic distortion. The calibrated radiance maps are then used to derive temperature maps of the laser-heated hotspots. For smaller heating spots, the radiance mapping approach reveals chromatic shifts that conventional spectro-radiometric methods cannot quantify. Ambient-pressure heating experiments confirm accurate temperature retrieval. At high pressure, application of the hyperspectral system to a platinum-heating experiment at 12 GPa demonstrates stable temperature reconstruction under steep thermal gradients. Beyond mitigating chromatic aberrations, the ability to diagnose optical artifacts separately from emissivity variations during controlled test experiments or in situ suggests a path toward more rigorous spectral emissivity analysis and improved modeling of thermal transport in laser-heated DAC experiments.

47 OTHER INSTRUMENTATION↗

Twelve and a Half Years of Observations of Centaurus A with RXTE

The Rossi X-ray Timing Explorer has observed the nearest radio galaxy, Centaurus A, in 13 intervals from 1996 August to 2009 February over the 3 - 200 keV band. Spectra accumulated over the 13 intervals were well described with an absorbed power law and an iron line. Cut-off power laws and Compton reflection from cold matter did not provide a better description. For the 2009 January observation we set a lower limit on the cutoff energy at over 2 MeV. The power spectral density function was generated from RXTE/ASM and PCA data as well as an XMM-Newton long look, and clear evidence for a break at 18(+18/-7) days (68% conf.) was seen. Given Cen A's high black hole mass and very low value of L(sub x)/L(sub Edd), the break was a factor of 17+/-9 times higher than the break frequency predicted by the McHardy and coworkers relation, which was empirically derived for a sample of objects, which are radio-quiet and accreting at relatively high values of L(sub bol)/L(sub Edd). We have interpreted our observations in the context of a clumpy molecular torus. The variability characteristics and the broadband spectral energy distribution, when compared to Seyferts, imply that the bright hard X-ray continuum emission may originate at the base of the jet, yet from behind the absorbing line of sight material, in contrast to what is commonly observed from blazars.

Rothschild, R. E.↗

Comparison of Eulerian Bin and Lagrangian Particle-Based Schemes in Simulations of Pi Chamber Dynamics and Microphysics

This paper presents a comparison of simulations applying either a traditional Eulerian bin microphysics or a novel particle-based Lagrangian approach to represent CCN activation and cloud droplet growth. The Eulerian microphysics solve the evolution equation for the spectral density function, whereas the Lagrangian approach follows computational particles referred to as superdroplets. Each superdroplet represents a multiplicity of natural droplets that makes the Lagrangian approach computationally feasible. The two schemes apply identical representation of CCN activation and use the same droplet growth equation; these make direct comparison between the two schemes practical. The comparison, the first of its kind, applies an idealized simulation setup motivated by laboratory experiments with the Pi Chamber and previous model simulations of the Pi Chamber dynamics and microphysics. The Pi Chamber laboratory apparatus considers interactions between turbulence, CCN activation, and cloud droplet growth in moist Rayleigh–Bénard convection. Simulated steady-state droplet spectra averaged over the entire chamber are similar, with the mean droplet concentration, mean radius, and spectral width close in Eulerian and Lagrangian simulations. Small differences that do exist are explained by the inherent differences between the two schemes and their numerical implementation. The local droplet spectra differ substantially, again in agreement with the inherent limitations of the theoretical foundation behind each approach. There is a general agreement between simulations and Pi Chamber observations, with simplifications of the CCN activation and droplet growth equation used in the simulations likely explaining specific differences.

54 ENVIRONMENTAL SCIENCES↗

Low-Luminosity AGN As Analogues of Galactic Black Holes in the Low/Hard State: Evidence from X-Ray Timing of NGC 4258

We present a broadband power spectral density function (PSD) measured from extensive RXTE monitoring data of the low-luminosity AGN NGC 4258, which has an accurate, maser-determined black hole mass of (3.9 plus or minus 0.1) x 10(exp 7) solar mass. We constrain the PSD break time scale to be greater than 4.5 d at greater than 90% confidence, which appears to rule out the possibility that NGC 4258 is an analogue of black hole X-ray binaries (BHXRBs) in the high/soft state. In this sense, the PSD of NGC 4258 is different to that of some more-luminous Seyferts, which appear similar to the PSDs of high/soft state X-ray binaries. This result supports previous analogies between LLAGN and X-ray binaries in the low/hard state based on spectral energy distributions, indicating that the AGN/BHXRB analogy is valid across a broad range of accretion rates.

Markowitz, A.↗

Chemical Compositions and Abundance Anomalies in Stellar Coronae ADP 99

New atomic data for tackling some of our spectra have been investigated by co-I Laming (NRL), including the effects of recombination on spectral line fluxes that are not included in, for example, the CHIANTI database models. Promising new progress has been made with modelling some of the recent abundance anomaly results in terms of Alven wave-driven separation of neutrals and ions in the upper chromosphere. The problems that existing models have is that they cannot simultaneously explain the low-FIP enhanced solar-like coronae and the high-FIP rich active coronae of RS CVn-like stars. The Alven wave model shows promise with both of these scenarios, with the fractionation or suppression of low-FIP ions depending on the characteristics of the chromosphere. This work is currently in the writing up stage. In summary, the work to-date is making good progress in mapping abundance anomalies as a function of spectral type and activity level. We are also making good progress with modelling that we will be able to test with our observational results. With one more year of effort, we'anticipate that the bulk of the work described above can be published, together with outstanding key studies on anomalies among the different active binaries.

Oliversen, Ronald J.↗

Comparison of Eulerian Bin and Lagrangian Particle-Based Microphysics in Simulations of Nonprecipitating Cumulus

A single nonprecipitating cumulus congestus setup is applied to compare droplet spectra grown by the diffusion of water vapor in Eulerian bin and particle-based Lagrangian microphysics schemes. Bin microphysics represent droplet spectral evolution applying the spectral density function. In the Lagrangian microphysics, computational particles referred to as superdroplets are followed in time and space with each superdroplet representing a multiplicity of natural cloud droplets. The same cloud condensation nuclei (CCN) activation and identical representation of the droplet diffusional growth allow the comparison. The piggybacking method is used with the two schemes operating in a single simulation, one scheme driving the dynamics and the other one piggybacking the simulated flow. Piggybacking allows point-by-point comparison of droplet spectra predicted by the two schemes. Overall, the results show the impact of inherent limitations of the two microphysics simulation methods, numerical diffusion in the Eulerian scheme and a limited number of superdroplets in the Lagrangian scheme. Numerical diffusion in the Eulerian scheme results in a more dilution of the cloud upper half and thus smaller cloud droplet mean radius. The Lagrangian scheme typically has larger spatial fluctuations of droplet spectral properties. A significantly larger mean spectral width in the bin microphysics across the entire cloud depth is the largest difference between the two schemes. A fourfold increase of the number of superdroplets per grid volume and a twofold increase of the spectral resolution and thus the number of bins have small impact on the results and provide only minor changes to the comparison between simulated cloud properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On-Orbit Calibration of ADEOS OCTS with an AVIRIS Underflight

The Ocean Color Temperature Scanner (OCTS) onboard the Advanced Earth Observation Satellite (ADEOS) was launched on August 17, 1996. Calibration of OCTS is required for use of the on-orbit measured data for retrieval of physical properties of the ocean. In the solar reflected portion of the electromagnetic spectrum, OCTS measures images with nominally 700-m spatial resolution through eight multispectral bands. The objective of this research was to establish the absolute radiometric calibration of OCTS on orbit through an underflight by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). AVIRIS is a NASA Earth-observing imaging spectrometer designed, built and operated by the Jet Propulsion Laboratory (JPL). AVIRIS acquires data from 20-km altitude on a NASA ER-2 aircraft, above most of the Earth's atmosphere. AVIRIS measures the solar reflected spectrum from 370 nm to 2500 nm through 224 contiguous spectral channels. The full width at half maximum (FWHM) of the spectral channels is nominally 10-nm. AVIRIS spectra are acquired as images of 11 km by up to 800 km extent with 20-m spatial resolution. The high spectral resolution of AVIRIS data allows direct convolution to the spectral response functions of the eight multispectral bands of OCTS. The high spatial resolution of AVIRIS data allows for spatial re-sampling of the data to match the ADEOS sensors spatial resolution. In addition, the AVIRIS high spatial resolution allows assessment of the scaling effects due to environmental factors of thin cirrus clouds, sub-pixel cloud cover, white caps, ocean foam, sun-glint, and bright-target adjacency. The platform navigation information recorded by AVIRIS allows calculation of the position and observation geometry of each spectrum for matching to the OCTS measurement. AVIRIS is rigorously characterized and calibrated in the laboratory prior to and following the flight season. The stability and repeatability of AVIRIS calibration have been validated through an extensive series of inflight calibration experiments. In the OCTS portion of the spectrum, using pre- and post-flight runway calibrations of AVIRIS coupled with the on-board calibrator an absolute calibration accuracy of better than 3% spectral, 2% radiometric, and 5% spatial, has been achieved. An analogous satellite underflight calibration experiment was performed with AVIRIS and the Optical Sensor (OPS) onboard the Japanese Earth Resources Satellite (JERS).

Green, Robert O.↗

On-Orbit Calibration of ADEOS OCTS with an AVIRIS Underflight

The Ocean Color Temperature Scanner (OCTS) onboard the Advanced Earth Observation Satellite (ADEOS) was launched on August 17, 1996. Calibration of OCTS is required for use of the on-orbit measured data for retrieval of physical properties of the ocean. In the solar reflected portion of the electromagnetic spectrum, OCTS measures images with nominally 700-m spatial resolution through eight multispectral bands. The objective of this research was to establish the absolute radiometric calibration of OCTS on orbit through an underflight by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). AVIRIS is a NASA earth-observing imaging spectrometer designed, built and operated by the Jet Propulsion Laboratory (JPL). AVIRIS acquires data from 20-km altitude on a NASA ER-2 aircraft, above most of the Earth's atmosphere. AVIRIS measures the solar reflected spectrum from 370 nm to 2500 nm through 224 contiguous spectral channels. The full width at half maximum (FWHM) of the spectral channels is nominally 10-nm. AVIRIS spectra are acquired as images of 11 km by up to 800 km extent with 20-m spatial resolution. The high spectral resolution of AVIRIS data allows direct convolution to the spectral response functions of the eight multispectral bands of OCTS. The high spatial resolution of AVIRIS data allows for spatial re-sampling of the data to match the ADEOS sensors spatial resolution. In addition, the AVIRIS high spatial resolution allows assessment of the scaling effects due to environmental factors of thin cirrus clouds, sub-pixel cloud cover, white caps, ocean foam, sun-glint, and bright-target adjacency. The platform navigation information recorded by AVIRIS allows calculation of the position and observation geometry of each spectrum for matching to the OCTS measurement. AVIRIS is rigorously characterized and calibrated in the laboratory prior to and following the flight season. The stability and repeatability of AVIRIS calibration have been validated through an extensive series of inflight calibration experiments. In the OCTS portion of the spectrum, using pre-and post-flight runway calibrations of AVIRIS coupled with the on-board calibrator an absolute calibration accuracy of better than 3% spectral, 2% radiometric and 5% spatial has been achieved. An analogous satellite underflight calibration experiment was performed with AVIRIS and the Optical Sensor (OPS) onboard the Japanese Earth Resources Satellite (JERS).

Green, Robert O.↗

Flexible nonstationary spatiotemporal modeling of high-frequency monitoring data

Many physical datasets are generated by collections of instruments that make measurements at regular time intervals. For such regular monitoring data, we extend the framework of half-spectral covariance functions to the case of nonstationarity in space and time and demonstrate that this method provides a natural and tractable way to incorporate complex behaviors into a covariance model. Further, we use this method with fully time-domain computations to obtain bona fide maximum likelihood estimators—as opposed to using Whittle-type likelihood approximations, for example—that can still be computed conveniently. Additionally, we apply this method to very high-frequency Doppler LIDAR vertical wind velocity measurements, demonstrating that the model can expressively capture the extreme nonstationarity of dynamics above and below the atmospheric boundary layer and, more importantly, the interaction of the process dynamics across it.

54 ENVIRONMENTAL SCIENCES↗

The 3D Recognition, Generation, Fusion, Update and Refinement (RG4) Concept

This paper describes an active (real time) recognition strategy whereby information is inferred iteratively across several viewpoints in descent imagery. We will show how we use inverse theory within the context of parametric model generation, namely height and spectral reflection functions, to generate model assertions. Using this strategy in an active context implies that, from every viewpoint, the proposed system must refine its hypotheses taking into account the image and the effect of uncertainties as well. The proposed system employs probabilistic solutions to the problem of iteratively merging information (images) from several viewpoints. This involves feeding the posterior distribution from all previous images as a prior for the next view. Novel approaches will be developed to accelerate the inversion search using novel statistic implementations and reducing the model complexity using foveated vision. Foveated vision refers to imagery where the resolution varies across the image. In this paper, we allow the model to be foveated where the highest resolution region is called the foveation region. Typically, the images will have dynamic control of the location of the foveation region. For descent imagery in the Entry, Descent, and Landing (EDL) process, it is possible to have more than one foveation region. This research initiative is directed towards descent imagery in connection with NASA's EDL applications. Three-Dimensional Model Recognition, Generation, Fusion, Update, and Refinement (RGFUR or RG4) for height and the spectral reflection characteristics are in focus for various reasons, one of which is the prospect that their interpretation will provide for real time active vision for automated EDL.

Maluf, David A.↗

Absorptive effects and classical black hole scattering

Abstract We describe an approach to incorporating the physical effects of the absorption of energy by the event horizon of black holes in the scattering amplitudes based post-Minkowskian, point-particle effective description. Absorptive dynamics are incorporated in a model-independent way by coupling the usual point-particle description to an invisible sector of gapless internal degrees-of-freedom. The leading order dynamics of this sector are encoded in the low-energy expansion of a spectral density function obtained by matching an absorption cross section in the ultraviolet description. This information is then recycled using the scattering amplitudes based Kosower-Maybee-O’Connell in-in formalism to calculate the leading absorptive contribution to the impulse and change in rest mass of a Schwarzschild black hole scattering with a second compact body sourcing a massless scalar, electromagnetic or gravitational field. The results obtained are in complete agreement with previous worldline Schwinger-Keldysh calculations and provide an alternative on-shell scattering amplitudes approach to incorporating horizon absorption effects in the gravitational two-body problem.

Physics↗

Determining Key Factors for the Open-Loop Control of Molecular Fragmentation Using Shaped Strong Fields

Pulse shaping has long been employed for tailoring femtosecond laser pulses to study and control the fragmentation of polyatomic molecules. In many cases, a physical explanation connecting the properties of the field to the observed control is difficult to ascertain. We utilized 80 bit binary spectral phase functions to parametrize and map the search space, gaining insight into which pulse parameters most impact the ion yield and fragmentation pattern for the relatively large triethylamine [N(C 2 H 5 ) 3 ] molecule. Pulse structures used to control the m/z 86 branching ratio beyond a simple intensity dependence are identified and compared to pump–probe results. All of these findings are explained in terms of control via a dissociative Rydberg state in the neutral molecule. This methodology may be used to discover new control mechanisms and shed light onto which pulse parameters most influence the interaction between strong field lasers and matter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collective optical Thomson scattering in pulsed-power driven high energy density physics experiments (invited)

Optical collective Thomson scattering is used to diagnose magnetized high energy density physics experiments at the Magpie pulsed-power generator at Imperial College London. The system uses an amplified pulse from the 2nd harmonic of a Nd:YAG laser (3 J, 8 ns, 532 nm) to probe a wide diversity of hightemperature plasma objects; with densities in the range of 10 17 -10 19 cm -3 and temperatures between 10 eV and a few keV. The scattered light is collected from 100 μm-scale volumes within the plasmas, which are imaged onto optical fiber arrays. Multiple collection systems observe these volumes from different directions, providing simultaneous probing with different scattering K-vectors (and different associated α-parameters, typically in the range 0.5 – 3) allowing independent measurements of separate velocity components of the bulk plasma flow. The fiber arrays are coupled to an imaging spectrometer with a gated ICCD. The spectrometer is configured to view the ion-acoustic waves (IAWs) of the collective Thomson scattered spectrum. Fits to the spectra with the theoretical spectral density function S(K,ω) yield measurements of the local plasma temperatures and velocities. Fitting is constrained by independent measurements of the electron density from laser interferometry, and the corresponding spectra for different scattering vectors. Furthermore, this TS diagnostic has been successfully implemented on a wide range of experiments, revealing temperature and flow velocity transitions across magnetized shocks, inside rotating plasma jets and imploding wire arrays, as well as providing direct measurements of drift velocities inside a magnetic reconnection current sheet.

47 OTHER INSTRUMENTATION↗

Dynamic embedding of effective harmonic normal mode vibrations in all-atomistic energy gap fluctuations: Case study of light harvesting 2 complex

Environmental effects in excitation energy transfer have mostly been modeled by baths of harmonic oscillators, but to what extent such modeling provides a reliable description of actual interactions between molecular systems and environments remains an open issue. Here, we address this issue by investigating fluctuations in the excitation energies of the light harvesting 2 complex using a realistic all-atomistic simulation of the potential energy surface. Our analyses reveal that molecular motions exhibit significant anharmonic features, even for underdamped intramolecular vibrations. In particular, we find that the anharmonicity contributes to the broadening of spectral densities and substantial overlaps between neighboring peaks, which complicates the meaning of mode frequencies constituting a bath model. Thus, we develop a strategy to construct a minimally underdamped harmonic bath that has a clear connection to all-atomistic dynamics by utilizing actual normal modes of molecules but optimizing their frequencies such that the resulting bath model can best reproduce the all-atomistic simulation results. By subtracting the underdamped contribution from the entire fluctuations, we also show that identifying a residual spectral density representing all other contributions with overdamped behavior is possible. We find that this can be fitted well with a well-established analytic form of a spectral density function or, alternatively, modeled as explicit time dependent fluctuations with muti-exponential or power law type correlation functions. We provide an assessment and the implications of these possibilities. The approach presented here can also serve as a general strategy to construct a simplified bath model that can effectively represent the underlying all-atomistic bath dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗