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All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Shallow and Deep Latent Heating Modes Over Tropical Oceans Observed with TRMM PR Spectral Latent Heating Data

The global hydrological cycle is central to the Earth's climate system, with rainfall and the physics of its formation acting as the key links in the cycle. Two-thirds of global rainfall occurs in the Tropics. Associated with this rainfall is a vast amount of heat, which is known as latent heat. It arises mainly due to the phase change of water vapor condensing into liquid droplets; three-fourths of the total heat energy available to the Earth's atmosphere comes from tropical rainfall. In addition, fresh water provided by tropical rainfall and its variability exerts a large impact upon the structure and motions of the upper ocean layer. Three-dimensional distributions of latent heating estimated from Tropical Rainfall Measuring Mission Precipitation Radar (TRMM PR)utilizing the Spectral Latent Heating (SLH) algorithm are analyzed. Mass-weighted and vertically integrated latent heating averaged over the tropical oceans is estimated as approx.72.6 J/s (approx.2.51 mm/day), and that over tropical land is approx.73.7 J/s (approx.2.55 mm/day), for 30degN-30degS. It is shown that non-drizzle precipitation over tropical and subtropical oceans consists of two dominant modes of rainfall systems, deep systems and congestus. A rough estimate of shallow mode contribution against the total heating is about 46.7 % for the average tropical oceans, which is substantially larger than 23.7 % over tropical land. While cumulus congestus heating linearly correlates with the SST, deep mode is dynamically bounded by large-scale subsidence. It is notable that substantial amount of rain, as large as 2.38 mm day-1 in average, is brought from congestus clouds under the large-scale subsiding circulation. It is also notable that even in the region with SST warmer than 28 oC, large-scale subsidence effectively suppresses the deep convection, remaining the heating by congestus clouds. Our results support that the entrainment of mid-to-lower-tropospheric dry air, which accompanies the large-scale subsidence is the major factor suppressing the deep convection. Therefore, representation of the realistic entrainment is very important for proper reproduction of precipitation distribution and resultant large-scale circulation.

Takayabu, Yukari N.↗
NASA NTRS2022

A Comparative Evaluation of Snowflake Particle Shape Estimation Techniques Used By the Precipitation Imaging Package (PIP), Multi-Angle Snowflake Camera (MASC), and Two-Dimensional Video Disdrometer (2DVD)

Measurements of snowflake particle shape are important for studying snow microphysics. While a number of instruments exist that are capable of measuring particle shape, this study focuses on the measurement techniques of three digital video disdrometers: the Precipitation Imaging Package (PIP), the Multi-Angle Snowflake Camera (MASC), and the Two-Dimensional Video Disdrometer (2DVD). To gain a better understanding of the relative strengths and weaknesses of these instruments and to provide a foundation upon which comparisons can be made between studies using data from different instruments, we perform a comparative analysis of the shape measurement algorithms employed by each of the three instruments by applying the algorithms to snowflake images captured by PIP during the ICE-POP 2018 field campaign. Our analysis primarily focuses on the measurement of the aspect ratio of either the particle itself, in the case of PIP and MASC, or of the particle bounding box, in the case of PIP and 2DVD. Both PIP and MASC use shape-fitting algorithms to measure aspect ratio. While our analysis of the MASC aspect ratio suggests that the measurements are reliable, our findings indicate that both the ellipse and rectangle aspect ratios produced by PIP underperformed considerably due to the shortcomings of the PIP shape-fitting techniques. We also demonstrate that reliable measurements of aspect ratio can be retrieved from PIP by reprocessing the raw PIP images using either the MASC ellipse-fitting algorithm or a tensor-based ellipse-fitting algorithm. Because of differences in instrument design, 2DVD produces measurements of particle horizontal and vertical extent rather than length and width. Furthermore, the 2DVD measurements of particle horizontal extent can be contaminated by horizontal particle motion. Our findings indicate that, although the correction technique used to remove the horizontal motion contamination performs remarkably well with snowflakes despite being designed for use with raindrops, the 2DVD measurements of particle horizontal extent are less reliable than those measured by PIP.

Charles N Helms↗
DOE OSTI2020

Stability Analysis of Inline ZFP Compression for Floating-Point Data in Iterative Methods

Currently, the dominating constraint in many high performance computing applications is data capacity and bandwidth, in both internode communications and even moreso in intranode data motion. A new approach to address this limitation is to make use of data compression in the form of a compressed data array. Storing data in a compressed data array and converting to standard IEEE-754 types as needed during a computation can reduce the pressure on bandwidth and storage. However, repeated conversions (lossy compression and decompression) introduce additional approximation errors, which need to be shown to not significantly affect the simulation results. Here, we extend recent work that analyzed the error of a single use of compression and decompression of the ZFP compressed data array representation to the case of time-stepping and iterative schemes, where an advancement operator is repeatedly applied in addition to the conversions. We show that the accumulated error for iterative methods involving fixed-point and time evolving iterations is bounded under standard constraints. An upper bound is established on the number of additional iterations required for the convergence of stationary fixed-point iterations. An additional analysis of traditional forward and backward error of stationary iterative methods using ZFP compressed arrays is also presented. The results of several 1D, 2D, and 3D test problems are provided to demonstrate the correctness of the theoretical bounds.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1992

Error Analysis of Combined Optical-Flow and Stereo Passive Ranging

The motion of an imaging sensor causes each imaged point of the seem to describe a time trajectory on the image plane. The trajectories of all imaged points are reminiscent of a flow (eg, of liquid) which is the source of the term "optical flow". Optical-flow ranging is a method by which the stream of two-dimensional images obtained from a forward-looking forward-moving passive sensor is used to compute range to points in the field of view. Another well-known ranging method consists of triangulation based on stereo images obtained from at least two stationary sensors. In this paper we analyze the potential accuracies of a combined optical flow and stereo passive-ranging system in the context of helicopter nap-of-the-earth obstacle avoidance. The Cramer-Rao lower bound (CRLB) is developed for the combined system under the assumption of a random angular misalignment common to both cameras of a stereo pair. It is shown that the range accuracy degradations caused by misalignment is negligible for a combined optical-flow and stereo system as compared with a monocular optical-flow system.

Barniv, Yair↗
NASA NTRSDate not supplied

Isolator Shock Train Response to Dual-Mode Scramjet Throttling-Like Forcing

Typical dual-mode scramjet designs employ an isolator component situated between the inlet and combustor. The isolator fluidically buffers the inlet from the combustor via the formation of a shock train, an interconnected series of shock-boundary layer interactions. The isolator is required during ramjet-engine operation and at the lower edges of the scramjet operational envelope. In an operational engine, transient behavior imposes fluidic dynamics due to attitude adjustments, combustor throttling, aberrant resonances within the combustor, etc. To accommodate these transients, the shock train adjusts on both temporal and spatial scales. Sufficiently large downstream pressure increases in the combustor play a critical role during unstart, whereby strong compression waves propagate upstream in the isolator to ultimately force the shock train out the inlet, if it cannot stabilize to the pressure increase. This critically reduces the engine mass flow rate, potentially causing a catastrophic reduction in thrust and loss of the vehicle. A nearly instantaneous unstart can, in principle, be predicted by a ratio of the normal shock pressure jump in an inviscid isolator. However, lower-magnitude perturbations, below this bound, also induce unstarts. Understanding the transient behavior inherent in unsteady isolator operation is critical to reducing safety margin in isolator length and refining engine control algorithms to improve engine performance. The Isolator Dynamics Research Lab (IDRL) is a cold-flow, direct-connect isolator facility ideal for assessing the fundamental fluid dynamics of shock trains. The internal flow of a scramjet isolator is modeled using a 2D, symmetric Mach 2.5 nozzle followed by a 695 mm long, 25.4x50.8 mm rectangular isolator test section. A blockage cone on a high-speed ball screw actuator downstream of the isolator is pulsed to simulate the throttling behavior in an operational combustor. Wall flush high-speed static pressure transducers detect the streamwise shock train within the isolator. Time delays between the onset of the throttling and the response motion of the shock train are analyzed to assess the controlling scales and parameters. From this analysis, the response time of the isolator shock train system is found to depend primarily on the isolator back pressure time-rate-of-change but quickly saturates to a maximum propagation speed along the isolator. These results inform dual-mode scramjet engine designers of the critical parameters and limits of an unstart resistant engine.

scramjet↗
NASA NTRS2000

A Dynamical Model for The Jupiter Thermocline

A new conceptual model for the observed banded wind structure of the giant outer planets is proposed, assuming a smoothly distributed potential vorticity (PV) atop a layer of deeply seated, latitudinally variable stratification. With a vanishing horizontal entropy contrast presumably enforced at the bottom of the flow layer by the underlying convection, the thermal-wind balance of observed cloud-top motions implies a mapping of constant potential temperature surfaces, nearly vertical at upper tropospheric levels, down to a deeper, flatter, but variably sloped 'thermocline.' For a generally colder-poleward distribution of isentropes consistent with the strong equatorial jets of both Jupiter and Saturn, this kind of mapping would also imply a poleward decreasing static stability. The proposed temperature-stability distribution is just the reverse of the Earth's troposphere, where the strongest latitudinal potential temperature gradients are at the bottom instead of the top, with static stability generally increasing toward the pole. The warmer-stabler correlation for Jupiter would be consistent, however, with a nearly monotonic distribution of PV from low to high latitudes, over planetary scales for which the planetary vorticity dominates the relative vorticity of the jets. In this way efficient PV mixing for the isentropically bounded thermocline can account for the dynamical maintenance of the cyclonic flanks of the equatorial jet. Over latitudinal intervals comparable to the internal deformation scale, however, the gradient of the absolute vorticity is dominated by the flow curvature, with the local latitudinal gradient of the static stability proportional to the local potential temperature gradient and therefore the local variation in geostrophic velocity. The resulting correlation of velocities and vorticity gradients implies an alternation of the flow over the internal deformation radius set by the vertical entropy contrast.

Allison, Michael↗
NASA NTRS1991

Error analysis of combined stereo/optical-flow passive ranging

The motion of an imaging sensor causes each imaged point of the scene to correspondingly describe a time trajectory on the image plane. The trajectories of all imaged points are reminiscent of a flow (e.g., of liquid) which is the source of the term 'optical flow'. Optical-flow ranging is a method by which the stream of two-dimensional images obtained from a forward-looking forward-moving passive sensor is used to compute depth (or range) to points in the field of view. Another well-known ranging method consists of triangulation based on stereo images obtained from at least two stationary sensors. In this paper we analyze the potential accuracies of a combined optical flow and stereo passive-ranging system in the context of helicopter nap-of-the-earth obstacle avoidance. The Cramer-Rao lower bound is developed for the combined system under the assumption of an unknown angular bias error common to both cameras of a stereo pair. It is shown that the depth accuracy degradations caused by a bias error is negligible for a combined optical-flow and stereo system as compared to a monocular optical-flow system.

Barniv, Yair↗
NASA NTRS2011

Lateral-Directional Parameter Estimation on the X-48B Aircraft Using an Abstracted, Multi-Objective Effector Model

The problem of parameter estimation on hybrid-wing-body aircraft is complicated by the fact that many design candidates for such aircraft involve a large number of aerodynamic control effectors that act in coplanar motion. This adds to the complexity already present in the parameter estimation problem for any aircraft with a closed-loop control system. Decorrelation of flight and simulation data must be performed in order to ascertain individual surface derivatives with any sort of mathematical confidence. Non-standard control surface configurations, such as clamshell surfaces and drag-rudder modes, further complicate the modeling task. In this paper, time-decorrelation techniques are applied to a model structure selected through stepwise regression for simulated and flight-generated lateral-directional parameter estimation data. A virtual effector model that uses mathematical abstractions to describe the multi-axis effects of clamshell surfaces is developed and applied. Comparisons are made between time history reconstructions and observed data in order to assess the accuracy of the regression model. The Cram r-Rao lower bounds of the estimated parameters are used to assess the uncertainty of the regression model relative to alternative models. Stepwise regression was found to be a useful technique for lateral-directional model design for hybrid-wing-body aircraft, as suggested by available flight data. Based on the results of this study, linear regression parameter estimation methods using abstracted effectors are expected to perform well for hybrid-wing-body aircraft properly equipped for the task.

Ratnayake, Nalin A.↗
DOE OSTI2023

Reduced dynamic complexity allows structure elucidation of an excited state of KRAS G13D

Localized dynamics of RAS, including regions distal to the nucleotide-binding site, is of high interest for elucidating the mechanisms by which RAS proteins interact with effectors and regulators and for designing inhibitors. Among several oncogenic mutants, methyl relaxation dispersion experiments reveal highly synchronized conformational dynamics in the active (GMPPNP-bound) KRAS G13D , which suggests an exchange between two conformational states in solution. Methyl and 31 P NMR spectra of active KRAS G13D in solution confirm a two-state ensemble interconverting on the millisecond timescale, with a major Pγ atom peak corresponding to the dominant State 1 conformation and a secondary peak indicating an intermediate state different from the known State 2 conformation recognized by RAS effectors. High-resolution crystal structures of active KRAS G13D and KRAS G13D -RAF1 RBD complex provide snapshots of the State 1 and 2 conformations, respectively. We use residual dipolar couplings to solve and cross-validate the structure of the intermediate state of active KRAS G13D , showing a conformation distinct from those of States 1 and 2 outside the known flexible switch regions. The dynamic coupling between the conformational exchange in the effector lobe and the breathing motion in the allosteric lobe is further validated by a secondary mutation in the allosteric lobe, which affects the conformational population equilibrium.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1993

Torque equilibrium attitudes for the Space Station

All spacecraft orbiting in a low earth orbit (LEO) experience external torques due to environmental effects. Examples of these torques include those induced by aerodynamic, gravity-gradient, and solar forces. It is the gravity-gradient and aerodynamic torques that produce the greatest disturbances to the attitude of a spacecraft in LEO, and large asymmetric spacecraft, such as the space station, are affected to a greater degree because the magnitude of the torques will, in general, be larger in proportion to the moments of inertia. If left unchecked, these torques would cause the attitude of the space station to oscillate in a complex manner and the resulting motion would destroy the micro-gravity environment as well as prohibit the orbiter from docking. The application of control torques will maintain the proper attitude, but the controllers have limited momentum capacity. When any controller reaches its limit, propellant must then be used while the device is reset to a zero or negatively-biased momentum state. Consequently, the rate at which momentum is accumulated is a significant factor in the amount of propellant used and the frequency of resupply necessary to operate the station. A torque profile in which the area curve for a positive torque is not equal to the area under the curve for a negative torque is 'biased,' and the consequent momentum build-up about that axis is defined as secular momentum because it continues to grow with time. Conversely, when the areas are equal, the momentum is cyclic and bounded. A Torque Equilibrium Attitude (TEA) is thus defined as an attitude at which the external torques 'balance' each other as much as possible, and which will result in lower momentum growth in the controllers. Ideally, the positive and negative external moments experienced by a spacecraft at the TEA would exactly cancel each other out and small cyclic control torques would be required only for precise attitude control. Over time, the only momentum build-up in the controllers would be due to electro-mechanical losses within the device. However, the atmospheric torques are proportional to the density of the atmosphere and the density varies with the orbital position, time of day, time of year, and the solar cycle. In addition, there are unmodeled disturbances and uncertainties in the mass and inertias. Therefore, there is no constant attitude that will completely balance the environmental torques and the dynamic TEA cannot be solved in closed form. The objective of this research was to determine a method to calculate a dynamic TEA such that the rate of momentum build-up in the controllers would be minimized and to implement this method in the MATRIX(x) simulation software by Integrated Systems, Inc.

Thompson, Roger C.↗
NASA NTRS1993

Theoretical constraints in the design of multivariable control systems

The theoretical constraints inherent in the design of multivariable control systems were defined and investigated. These constraints are manifested by the system transmission zeros that limit or bound the areas in which closed loop poles and individual transfer function zeros may be placed. These constraints were investigated primarily in the context of system decoupling or non-interaction. It was proven that decoupling requires the placement of closed loop poles at the system transmission zeros. Therefore, the system transmission zeros must be minimum phase to guarantee a stable decoupled system. Once decoupling has been accomplished, the remaining part of the system exhibits transmission zeros at infinity, so nearly complete design freedom is possible in terms of placing both poles and zeros of individual closed loop transfer functions. A general, dynamic inversion model following system architecture was developed that encompasses both the implicit and explicit configuration. Robustness properties are developed along with other attributes of this type of system. Finally, a direct design is developed for the longitudinal-vertical degrees of freedom of aircraft motion to show how a direct lift flap can be used to improve the pitch-heave maneuvering coordination for enhanced flying qualities.

Rynaski, E. G.↗
NASA NTRS1994

Interactions between nested sunspots. 1: The formation and breakup of a delta-type sunspot

We investigate a nest of sunspots in which three ordinary bipolar pairs of sunspots are aligned collinearly. The usual spreading action of the growing regions brings two spots of leading polarity together (p-p collision) and forces the leading and trailing spots of the two interior regions to overlap inot a single penumbra (p-f collision), thus forming a delta-spot. We examine digitally processed images from the Ottawa River Solar Observatory of two related events inside the delta-spot 5 days after the p-f collision begins: the violent disruption of the f-umbra, and the formation in less than a day of an hydrogen-alpha filament. The evolutionary changes in shape, area, relative motions, and brightness that we measure for each spot in the elongated nest are more compatible with Parker's (1979a) hypothesis of a sunspot as a cluster of flux tubes held together by downdrafts than with the notion of a sunspot as a monolithic plug of magnetic flux. From chromospheric developments over the delta-spot, we show that a shearing motion along a polarity inversion is more effective than convergence for creating a chromospheric filament. We invoke the release of an instability, triggered by a sequence of processes lasting 1 day or more, to explain the disruption of the f-umbra in this delta-spot. We show that the sequence is initiated when the colliding p-f umbrae reach a critical separation around 3200 +/- 200 km. We present a descriptive model in which the reconnected magnetic fields block vertical transport of convective heat flux just beneath the photosphere. We observe the formation of an unusual type of penumbra adjacent to the f-polarity portion of this delta-spot just before its disruption. A tangential penumbral band grows out of disordered matter connected to the f-umbra. We present this as evidence for the extrusion of umbral magnetic flux by thermal plumes rising through a loosely bound umbra.

Gaizauskas, V.↗
NASA NTRS1995

Determination of stability and control derivatives from the NASA F/A-18 HARV from flight data using the maximum likelihood method

This report is a compilation of PID (Proportional Integral Derivative) results for both longitudinal and lateral directional analysis that was completed during Fall 1994. It had earlier established that the maneuvers available for PID containing independent control surface inputs from OBES were not well suited for extracting the cross-coupling static (i.e., C(sub N beta)) or dynamic (i.e., C(sub Npf)) derivatives. This was due to the fact that these maneuvers were designed with the goal of minimizing any lateral directional motion during longitudinal maneuvers and vice-versa. This allows for greater simplification in the aerodynamic model as far as coupling between longitudinal and lateral directions is concerned. As a result, efforts were made to reanalyze this data and extract static and dynamic derivatives for the F/A-18 HARV (High Angle of Attack Research Vehicle) without the inclusion of the cross-coupling terms such that more accurate estimates of classical model terms could be acquired. Four longitudinal flights containing static PID maneuvers were examined. The classical state equations already available in pEst for alphadot, qdot and thetadot were used. Three lateral directional flights of PID static maneuvers were also examined. The classical state equations already available in pEst for betadot, p dot, rdot and phi dot were used. Enclosed with this document are the full set of longitudinal and lateral directional parameter estimate plots showing coefficient estimates along with Cramer-Rao bounds. In addition, a representative time history match for each type of meneuver tested at each angle of attack is also enclosed.

Napolitano, Marcello R.↗
NASA NTRS2015

The Structure, Anharmonic Vibrational Frequencies, and Intensities of NNHNN+

A semi-global potential energy surface (PES) and quartic force field (QFF) based on fitting high-level electronic structure energies are presented to describe the structures and spectroscopic properties of NNHNN+. The equilibrium structure of NNHNN+ is linear with the proton equidistant between the two nitrogen groups and thus of D(sub ∞h) symmetry. Vibrational second-order perturbation theory (VPT2) calculations based on the QFF fails to describe the proton “rattle” motion, i.e., the antisymmetric proton stretch, due to the very flat nature of PES around the global minimum, but performs properly for other modes with sharper potential wells. Vibrational self-consistent field/virtual state configuration interaction (VSCF/VCI) calculations using a version of MULTIMODE without angular momentum terms successfully describe this motion and predict the fundamental to be at 759 cm(exp -1). This is in good agreement with the value of 746 cm(exp -1) from a fixed-node diffusion Monte Carlo calculation and the experimental Ar-tagged result of 743 cm(exp -1). Other VSCF/VCI energies are in good agreement with other experimentally reported ones. Both double-harmonic intensity and rigorous MULTIMODE intensity calculations show the proton transfer fundamental has a very strong intensity.

Astrochemistry↗
DOE OSTI2020

The effects of stress, temperature and facet structure on growth of { 10 1 ¯ 2 } twins in Mg: a molecular dynamics and phase field study

The present study focuses on the roles of structure, stress and temperature on the mobility of facets bounding twin domains and on the overall impact on the growth kinetics of { 10 1 ¯ 2 } twins in Mg. We first use molecular dynamics simulations (MD) to study the relationship between interface structures, stress, temperature and mobility. As facets can exhibit distinct atomic scale structures, we also quantify the effect of stress relaxation mediated by misfit dislocations on the mobility of the basal-prismatic interface. The information gathered for ten different facets is used to calibrate an anisotropic phase field model predicting the effects of temperature and stress on the kinetics and shape of a growing { 10 1 ¯ 2 } 3D twin, by comparison with MD data. The comparative analysis suggests that, as compared to simulations of individual facets, the effective mobility of facets can be significantly different during growth of a 3D twin. This can be attributed to the complex three-dimensional internal stress state of the twin and to coupling in facet motion triggered by facet junctions. As such, by directly fitting both the twin growth kinetics and morphology as predicted by MD for different stresses and temperatures, we can identify a limited set of rate-limiting facets that control twin growth and morphology, and measure their effective mobility.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Beyond the Condon limit: Condensed phase optical spectra from atomistic simulations

While dark transitions made bright by molecular motions determine the optoelectronic properties of many materials, simulating such non-Condon effects in condensed phase spectroscopy remains a fundamental challenge. We derive a Gaussian theory to predict and analyze condensed phase optical spectra beyond the Condon limit. Our theory introduces novel quantities that encode how nuclear motions modulate the energy gap and transition dipole of electronic transitions in the form of spectral densities. By formulating the theory through a statistical framework of thermal averages and fluctuations, we circumvent the limitations of widely used microscopically harmonic theories, allowing us to tackle systems with generally anharmonic atomistic interactions and non-Condon fluctuations of arbitrary strength. We show how to calculate these spectral densities using first-principles simulations, capturing realistic molecular interactions and incorporating finite-temperature, disorder, and dynamical effects. Our theory accurately predicts the spectra of systems known to exhibit strong non-Condon effects (phenolate in various solvents) and reveals distinct mechanisms for electronic peak splitting: timescale separation of modes that tune non-Condon effects and spectral interference from correlated energy gap and transition dipole fluctuations. We further introduce analysis tools to identify how intramolecular vibrations, solute–solvent interactions, and environmental polarization effects impact dark transitions. Moreover, we prove an upper bound on the strength of cross correlated energy gap and transition dipole fluctuations, thereby elucidating a simple condition that a system must follow for our theory to accurately predict its spectrum.

Chemistry↗
DOE OSTI2025

Orientation-dependent enhanced ionization in acetylene revealed by ultrafast cross-polarized pulse pairs

We investigate the orientation dependence of enhanced ionization (EI) during strong-field-driven nuclear motion in acetylene (C 2 ⁢H 2 ). Here, we both initiate and probe molecular dynamics in acetylene with intense 6-fs cross-polarized pulse pairs, separated by a variable delay. Following multiple ionization by the first pulse, acetylene undergoes simultaneous elongation of the carbon-carbon and carbon-hydrogen bonds, enabling further ionization by the second pulse and the formation of a very highly charged state, [C 2 ⁢H 2 ] 6+ . At small interpulse delays (< 20 fs), this enhancement occurs when the molecule is aligned to the probe pulse. Conversely, at large delays (> 40 fs), formation of [C 2 ⁢H 2 ] 6+ occurs when the molecule is aligned to the pump pulse. By analyzing the polarization and time dependence of sequentially ionized [C 2 ⁢H 2 ] 6+ , we resolve two transient alignments that both contribute to a large increase in the multiple ionization yield. In conclusion, this cross-polarized pulse pair scheme uniquely enables selective probing of deeply bound orbitals, providing new insights on orientation-dependent EI in highly charged hydrocarbons.

Atomic & molecular clusters↗
DOE OSTI2020

The charge reduction rate for multiply charged polymer ions via ion–ion recombination at atmospheric pressure

The charge reduction of multiply charged macromolecular ions via recombination with small ions in the gas phase is commonly employed to modulate the charge on macromolecules prior to mass spectrometric and mobility analyses. We employ a recently developed continuum-Molecular Dynamics (MD) calculation approach to determine the recombination rate coefficient of multiply charged (1 to 7 excess positive charged) polyethylene glycol ions (mass of 4600 Da) with smaller singly charged anions, modeled as NO 2 – ions. The continuum-MD approach accounts explicitly for the influence of the background gas on the recombination process, accounts explicitly for ion translational, vibrational, and rotational motion, and enables recombination rate coefficient calculation in nitrogen near atmospheric pressure, wherein neither low pressure nor high pressure recombination theories are strictly applicable. Continuum-MD simulations yield recombination rate coefficients near 3.9 × 10 –14 m 3 s –1 for singly charged ions, increasing to 3.0 × 10 –11 m 3 s –1 for the +7 ion. Pre-existing collision rate coefficient expressions for rigid ions are found to be within a factor of 2–5 of calculations for all charge states, but their use requires knowledge of an appropriate collision distance, which is not well-defined for flexible polymer ions. Continuum-MD-inferred rate coefficients are incorporated into a model of charge reduction, and the charge state distribution versus anion concentration determined with it is compared to charge reduction measurements made via atmospheric pressure differential mobility analysis. Furthermore, good agreement is observed between simulations and experiments; although results are extremely sensitive to the recombination rate coefficients, experimental results are bound by models utilizing rates within a factor of 2 (0.5–2.0×) of the continuum-MD rates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗