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Perturbations in Brain Functional Connectivity Patterns After Waking From Slow Wave Sleep Under Different Cognitive States

Sleep inertia refers to the state of transition between sleep and wake characterized by impaired alertness, confusion, and reduced cognitive and behavioral performance. While the behavioral symptoms of sleep inertia are well described, the neurological changes that lead to this state remain elusive. Here, to understand the state of sleep inertia and the reorganization that the brain undergoes, we took a graph theoretical approach and compared the EEG derived brain connectivity patterns before sleep and after waking up while participants (n = 10) performed multiple tasks that differed in cognitive complexities. We focused on how the degree and the clustering coefficient of brain regions (EEG sensors) change immediately after participants wake up from slow wave sleep. During a psychomotor vigilance task (PVT), designed to assess vigilant attention, we find that the brain regions with strong network connectivity (degree) before sleep show a reduction in connectivity after waking. In contrast, those with low connectivity before sleep have greater connectivity after waking. The regions that undergo these changes are specific to each participant and these findings are unique to the beta frequency range, which plays a key role in sensorimotor functioning and preserving the current state of the brain. Moreover, in tasks that required inhibitory control and arithmetic reasoning, we found that only regions with weak connectivity before sleep exhibited more connections after waking, but regions with high connectivity prior to sleeping remained unchanged, highlighting task specific effects. Furthermore, we find that during the PVT, the clustering coefficient within low frequency oscillations of the brain is reduced upon waking while it remains unchanged during other tasks. These results suggest that the connections between regions that are lost after abrupt awakening can be reallocated to other regions in order to renormalize the brain. However, this response may only be evident during specific cognitive states and may be more nuanced during complex task performance.

sleep inertia↗
DOE OSTI2016

Patterned growth of p-type MoS 2 atomic layers using sol-gel as precursor

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to the incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2 , which shows strong rectifying behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cluster environment quenches the star formation of low-mass satellite galaxies from the inside-out

ABSTRACT Environment plays a critical role in the star formation history of galaxies. Tidal and hydrodynamical stripping, prominent in cluster environment, can remove the peripheral gas of galaxies and star formation may thus be environmentally suppressed from the outside-in. We revisit the environmental dependence of the radial gradient of specific star formation rate (sSFR) profile. We probe the radial gradient by using the archival spectral indices D4000n and HδA measured from SDSS fibre spectra, to indicate central sSFR and the total sSFR from fitting the spectral energy distribution. Despite the low spatial resolution, the wealth of SDSS data allows to disentangle the dependences on stellar mass, sSFR, and environment. We find that low-mass satellite galaxies in the mass range $9\lt \mathrm{log}\, \mathcal {M}_{\star }/\mathcal {M}_{\odot }\lt 9.8$ on average quench in more inside-out pattern compared to isolated galaxies matched in mass, sSFR, and fibre coverage. This environmental effect is particularly strong for galaxies below the star formation main sequence, and peaks for those in the core of massive clusters where the phase-space diagram reveals clear links between the inside-out quenching and orbital properties. Our results suggest that both tidal and hydrodynamical interactions in cluster environment suppress the star formation of satellites mainly from the inside-out. As accreted gas of low angular momentum from hot gas haloes is an important source for replenishing central gas reservoir, we discuss how gas stripping in clusters may lead to starvation and cause inside-out quenching when the outer star-forming discs are not significantly affected.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Maximizing Electron Exchange in a [F 3 ] Cluster

The one-electron reduction of ( tbs L)Fe 3 (thf) 1 furnishes [M][( tbs L)Fe 3 ] ([M] + = [(18-C-6)K(thf) 2 ] + (1, 76%) or [(crypt-222)K] + (2, 54%)). Upon reduction, the ligand tbs L 6- rearranges around the triiron core to adopt an almost ideal C 3 -symmetry. Accompanying the ( tbs L) ligand rearrangement, the THF bound to the neutral starting material is expelled, and the Fe–Fe distances within the trinuclear cluster contract by ~0.13 Å in 1. Variable-temperature magnetic susceptibility data indicates a well-isolated spin ground state that persists to room temperature. Slow magnetic relaxation is observed at low temperature as evidenced by the out-of-phase component of the alternating current (ac) magnetic susceptibility data and by the appearance of hyperfine splitting in the zero-field 57 Fe Mössbauer spectra at 4.2 K. Analysis of the ac magnetic susceptibility yields an effective spin reversal barrier (U eff ) of 22.6(2) cm -1 , nearly matching the theoretical barrier of 38.7 cm -1 calculated from the axial zero-field splitting parameter (D = -1.29 cm -1 ) extracted from the reduced magnetization data. A polycrystalline sample of 1 displays three sextets in the Mössbauer spectrum at 4.2 K (H ext = 0) which converge to a single six-line pattern in a frozen 2-MeTHF glass sample, indicating a unique iron environment and thus strong electron delocalization. The spin ground state and ligand rearrangement are discussed within the framework of a fully delocalized cluster exhibiting strong double and direct exchange interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Attractor comparisons based on density

Recognizing a chaotic attractor can be seen as a problem in pattern recognition. Some feature vector must be extracted from the attractor and used to compare to other attractors. The field of machine learning has many methods for extracting feature vectors, including clustering methods, decision trees, support vector machines, and many others. In this work, feature vectors are created by representing the attractor as a density in phase space and creating polynomials based on this density. Density is useful in itself because it is a one dimensional function of phase space position, but representing an attractor as a density is also a way to reduce the size of a large data set before analyzing it with graph theory methods, which can be computationally intensive. The density computation in this paper is also fast to execute. In this paper, as a demonstration of the usefulness of density, the density is used directly to construct phase space polynomials for comparing attractors. Comparisons between attractors could be useful for tracking changes in an experiment when the underlying equations are too complicated for vector field modeling.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Successional trajectories of rhizosphere bacterial communities over consecutive seasons

It is well known that rhizosphere microbiomes differ from those of surrounding soil, and yet we know little about how these root-associated microbial communities change through the growing season and between seasons. We analyzed the response of soil bacteria to roots of the common annual grass Avena fatua over two growing seasons using high-throughput sequencing of 16S rRNA genes. Over the two periods of growth, the rhizosphere bacterial communities followed consistent successional patterns as plants grew, although the starting communities were distinct. Succession in the rhizosphere was characterized by a significant decrease in both taxonomic and phylogenetic diversity relative to background soil communities, driven by reductions in both richness and evenness of the bacterial communities. Plant roots selectively stimulated the relative abundance of Alphaproteobacteria , Betaproteobacteria , and Bacteroidetes but reduced the abundance of Acidobacteria , Actinobacteria , and Firmicutes . Taxa that increased in relative abundance in the rhizosphere soil displayed phylogenetic clustering, suggesting some conservation and an evolutionary basis for the response of complex soil bacterial communities to the presence of plant roots. The reproducibility of rhizosphere succession and the apparent phylogenetic conservation of rhizosphere competence traits suggest adaptation of the indigenous bacterial community to this common grass over the many decades of its presence. We document the successional patterns of rhizosphere bacterial communities associated with a “wild” annual grass, Avena fatua , which is commonly a dominant plant in Mediterranean-type annual grasslands around the world; the plant was grown in its grassland soil. Most studies documenting rhizosphere microbiomes address “domesticated” plants growing in soils to which they are introduced. Rhizosphere bacterial communities exhibited a pattern of temporal succession that was consistent and repeatable over two growing seasons. There are few studies assessing the reproducibility over multiple seasons. Through the growing season, the rhizosphere community became progressively less diverse, likely reflecting root homogenization of soil microniches. Phylogenetic clustering of the rhizosphere dynamic taxa suggests evolutionary adaptation to Avena roots. The reproducibility of rhizosphere succession and the apparent phylogenetic conservation of rhizosphere competence traits suggest adaptation of the indigenous bacterial community to this common grass over the many decades of its presence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations

Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf–O or Hf–B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cluster quantum chemical calculations on these systems. We compute full potential energy curves, excitation energies, ionization energies, electronic configurations, and spectroscopic parameters with large quadruple-ζ and quintuple-ζ quality correlation consistent basis sets. We also investigate equilibrium chemical bonding patterns and effects of correlating core electrons on property predictions. Differences in the ground state electron configuration of HfB(X 4 Σ - ) and HfO(X 1 Σ + ) lead to a significantly stronger bond in HfO than HfB, as judged by both dissociation energies and equilibrium bond distances. We extend our analysis to the chemical bonding patterns of the isovalent HfX (X = O, S, Se, Te, and Po) series and observe similar trends. We also note a linear trend between the decreasing value of the dissociation energy (D e ) from HfO to HfPo and the singlet–triplet energy gap (ΔE S–T ) of the molecule. Finally, we compare these benchmark results to those obtained using density functional theory (DFT) with 23 exchange–correlation functionals spanning multiple rungs of “Jacob’s ladder.” When comparing DFT errors to coupled cluster reference values on dissociation energies, excitation energies, and ionization energies of HfB and HfO, we observe semi-local generalized gradient approximations to significantly outperform more complex and high-cost functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

A Comprehensive Search for Stable Pt-Pd Nanoalloy Configurations and Their Use as Tunable Catalysts

Using density-functional theory, we predict stable alloy configurations (ground states) for a 1 nm Pt–Pd cuboctahedral nanoparticle across the entire composition range and demonstrate their use as tunable alloy catalysts via hydrogen-adsorption studies. Unlike previous works, we use simulated annealing with a cluster expansion Hamiltonian to perform a rapid and comprehensive search that encompasses both high and low-symmetry configurations. The ground states show Pt(core)–Pd(shell) type configurations across all compositions but with specific Pd patterns. For catalysis studies at room temperatures, the ground states are more realistic structural models than the commonly assumed random alloy configurations. Using the ground states, we reveal that the hydrogen adsorption energy increases (decreases) monotonically with at. % Pt for the {111} hollow ({100} bridge) adsorption site. Such trends are useful for designing tunable Pd–Pt nanocatalysts for the hydrogen evolution reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The effect of Ni addition on the structure of Pt–Sn/C nanoparticles by electron microscopy

Highlights: • A typical Pt/SnO{sub 2} core–shell structure is present in Pt–Sn. • The most of SnO{sub 2} species are likely clustered in Pt–Sn. • SnO{sub 2} nanoparticles prefer to locate close to Pt–Sn–Ni nanoclusters. • Main crystallographic structures are either cubic Pt or PtSn{sub 2}. - Abstract: Carbon supported bimetallic Pt–Sn and trimetallic Pt–Sn–Ni nanoparticles were synthesized by Bönnemann's colloidal precursor method and characterized by high-resolution transmission electron microscopy (HR-TEM) and energy dispersive X-ray analysis (EDX) techniques. HR-TEM and EDX results demonstrated that SnO{sub 2} nanoparticles tend to form clusters in Pt–Sn/C; however, the presence of Ni in the Pt–Sn/C gives rise to an induced interaction between SnO{sub 2} and Pt nanoparticles. Electron diffraction patterns of Pt–Sn–Ni/C showed that either cubic Pt or PtSn{sub 2} structures are present. From the selected area EDX analysis, it was found that both of these structures contain Sn. This suggests that Pt–Sn–Ni/C nanoparticles may be partially covered by Sn-richer PtSn{sub 2} alloyed structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Transcriptional networks underlying a primary ovarian insufficiency disorder in alligators naturally exposed to EDCs

Interactions between the endocrine system and environmental contaminants are responsible for impairing reproductive development and function. Despite the taxonomic diversity of affected species and attendant complexity inherent to natural systems, the underlying signaling pathways and cellular consequences are mostly studied in lab models. To resolve the genetic and endocrine pathways that mediate affected ovarian function in organisms exposed to endocrine disrupting contaminants in their natural environments, we assessed broad-scale transcriptional and steroidogenic responses to exogenous gonadotropin stimulation in juvenile alligators (Alligator missippiensis) originating from a lake with well-documented pollution (Lake Apopka, FL) and a nearby reference site (Lake Woodruff, FL). Here, we found that individuals from Lake Apopka are characterized by hyperandrogenism and display hyper-sensitive transcriptional responses to gonadotropin stimulation when compared to individuals from Lake Woodruff. Site-specific transcriptomic divergence appears to be driven by wholly distinct subsets of transcriptional regulators, indicating alterations to fundamental genetic pathways governing ovarian function. Consistent with broad-scale transcriptional differences, ovaries of Lake Apopka alligators displayed impediments to folliculogenesis, with larger germinal beds and decreased numbers of late-stage follicles. After resolving the ovarian transcriptome into clusters of co-expressed genes, most site-associated modules were correlated to ovarian follicule phenotypes across individuals. However, expression of two site-specific clusters were independent of ovarian cellular architecture and are hypothesized to represent alterations to cell-autonomous transcriptional programs. Collectively, our findings provide high resolution mapping of transcriptional patterns to specific reproductive function and advance our mechanistic understanding regarding impaired reproductive health in an established model of environmental endocrine disruption.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

Massively parallel X-ray scattering simulations

Although present X-ray scattering techniques can provide tremendous information on the nano-structural properties of materials that are valuable in the design and fabrication of energy-relevant nano-devices, a primary challenge remains in the analyses of such data. In this paper we describe a high-performance, flexible, and scalable Grazing Incidence Small Angle X-ray Scattering simulation algorithm and codes that we have developed on multi-core/CPU and many-core/GPU clusters. We discuss in detail our implementation, optimization and performance on these platforms. Our results show speedups of ~125x on a Fermi-GPU and ~20x on a Cray-XE6 24-core node, compared to a sequential CPU code, with near linear scaling on multi-node clusters. To our knowledge, this is the first GISAXS simulation code that is flexible to compute scattered light intensities in all spatial directions allowing full reconstruction of GISAXS patterns for any complex structures and with highresolutions while reducing simulation times from months to minutes.

Sarje, Abhinav↗
DOE OSTI2012

Fast and Accurate Simulation of the Cray XMT Multithreaded Supercomputer

Irregular applications, such as data mining and analysis or graph-based computations, show unpredictable memory/network access patterns and control structures. Highly multithreaded architectures with large processor counts, like the Cray MTA-1, MTA-2 and XMT, appear to address their requirements better than commodity clusters. However, the research on highly multithreaded systems is currently limited by the lack of adequate architectural simulation infrastructures due to issues such as size of the machines, memory footprint, simulation speed, accuracy and customization. At the same time, Shared-memory MultiProcessors (SMPs) with multi-core processors have become an attractive platform to simulate large scale machines. In this paper, we introduce a cycle-level simulator of the highly multithreaded Cray XMT supercomputer. The simulator runs unmodified XMT applications. We discuss how we tackled the challenges posed by its development, detailing the techniques introduced to make the simulation as fast as possible while maintaining a high accuracy. By mapping XMT processors (ThreadStorm with 128 hardware threads) to host computing cores, the simulation speed remains constant as the number of simulated processors increases, up to the number of available host cores. The simulator supports zero-overhead switching among different accuracy levels at run-time and includes a network model that takes into account contention. On a modern 48-core SMP host, our infrastructure simulates a large set of irregular applications 500 to 2000 times slower than real time when compared to a 128-processor XMT, while remaining within 10\% of accuracy. Emulation is only from 25 to 200 times slower than real time.

Cray XMT↗
NASA NTRS1982

Helium abundance enhancements in the solar wind

Evidence for a link between helium enhancements at 1 AU and transient coronal mass ejections is provided by the statistical analysis of 73 large helium abundance enhancement observations made by IMPs 6, 7 and 8 over 1972-1978. These events, in which helium abundance enhancement is greater than about 10%, are sporadic, sometimes clustered in time, occur approximately in phase with the solar cycle, and nearly 50% of them are associated with interplanetary shocks and/or geomagnetic activity sudden commencements. The plasma pattern associated with them is nevertheless independent of shock occurrence, and features high magnetic field strength, low alpha-proton velocity difference, and low proton temperature, suggesting that the enhancement is embedded in a closed, magnetically dominated structure that expands adiabatically. Evidence of an association between helium enhancement at 1 AU and type II and IV radio bursts in the corona is presented.

Borrini, G.↗
NASA NTRS1993

Ion mobility spectrometry of hydrazine, monomethylhydrazine, and ammonia in air with 5-nonanone reagent gas

Hydrazine (HZ) and monomethylhydrazine (MMH) in air were monitored continuously using a hand-held ion mobility spectrometer equipped with membrane inlet, 63Ni ion source, acetone reagent gas, and ambient temperature drift tube. Response characteristics included detection limit, 6 ppb; linear range, 10-600 ppb; saturated response, >2 ppm; and stable response after 15-30 min. Ammonia interfered in hydrazines detection through a product ion with the same drift time as that for MMH and HZ. Acetone reagent gas was replaced with 5-nonanone to alter drift times of product ions and separate ammonia from MMH and HZ. Patterns in mobility spectra, ion identifications from mass spectra, and fragmentation cross-sections from collisional-induced dissociations suggest that drift times are governed by ion-cluster equilibria in the drift region of the mobility spectrometer. Practical aspects including calibration, stability, and reproducibility are reported from the use of a hand-held mobility spectrometer on the space shuttle Atlantis during mission STS-37.

Flight Experiment↗
NASA NTRS2017

A Network-Based Algorithm for Clustering Multivariate Repeated Measures Data

The National Aeronautics and Space Administration (NASA) Astronaut Corps is a unique occupational cohort for which vast amounts of measures data have been collected repeatedly in research or operational studies pre-, in-, and post-flight, as well as during multiple clinical care visits. In exploratory analyses aimed at generating hypotheses regarding physiological changes associated with spaceflight exposure, such as impaired vision, it is of interest to identify anomalies and trends across these expansive datasets. Multivariate clustering algorithms for repeated measures data may help parse the data to identify homogeneous groups of astronauts that have higher risks for a particular physiological change. However, available clustering methods may not be able to accommodate the complex data structures found in NASA data, since the methods often rely on strict model assumptions, require equally-spaced and balanced assessment times, cannot accommodate missing data or differing time scales across variables, and cannot process continuous and discrete data simultaneously. To fill this gap, we propose a network-based, multivariate clustering algorithm for repeated measures data that can be tailored to fit various research settings. Using simulated data, we demonstrate how our method can be used to identify patterns in complex data structures found in practice.

Koslovsky, Matthew↗
NASA NTRS2017

Covariability of Climate and Streamflow in the Upper Rio Grande from Interannual to Interdecadal Timescales

Study region: The Upper Rio Grande (URG) flows from its headwaters in Colorado, U.S., and provides an important source of water to millions of people in the U.S. states of Colorado, New Mexico, Texas, and also Mexico. Study focus: We reassess the explanatory power of the relationship of sea surface temperatures (SST) on URG streamflow variability on interannual to interdecadal timescales. We find a significant amount of the variance of spring-summer URG streamflow cannot be fully explained by SST. New hydrological insights: We find that the interdecadal teleconnection between SST and streamflow is more clear than on interannual timescales. The highest ranked years tend to be clustered during positive phases of the Pacific Decadal Oscillation (PDO). During the periods of decadal high flow (1900-1920, and 1979-1995), Pacific SST resembles a positive PDO pattern and the Atlantic a negative Atlantic Multidecadal Oscillation (AMO) pattern; an interbasin pattern shown in prior studies to be conducive to high precipitation and streamflow. To account for the part of streamflow variance not explained by SST, we analyze atmospheric Reanalysis data for the months preceding the highest spring-summer streamflow events. A variety of atmospheric configurations are found to precede the highest flow years through anomalous moisture convergence. This lack of consistency suggests that, on interannual timescales, weather and not climate can dominate the generation of high streamflow events.

AMO↗
NASA NTRS2018

Agricultural Burning and Air Quality over Northern India: A Synergistic Analysis Using NASA's A-Train Satellite Data and Ground Measurements

In the recent years, New Delhi, the capital city of India, has ranked among the most polluted cities in the world regarding its air quality related to the submicron Particulate Matter (PM(sub 2.5)). Using NASA's A-train satellite data (MODIS, OMI, and CALIOP), ground-level PM2.5 measured in New Delhi (2013-2016), and back-trajectory calculations, we show that the PM(sub 2.5). over New Delhi is strongly affected by the agricultural fires in the northwestern Indian states of Punjab and Haryana during the post-monsoon season (October and November). The mass concentration of PM2.5 escalates from ~50 μg m(exp -3) measured prior to the onset of residue burning in early October to as high as 300 μg m(exp -3) (24-hour averaged, 7- day running mean) during the peak burning period in early November. A linear regression analysis reveals that the variations in PM(sub 2.5) over New Delhi can be attributed to the concurrent changes in the satellite retrievals of fire counts and aerosols over the crop burning area. The back-trajectory analysis shows that most clusters (> 80%) of the northwesterly flow near the ground intercepted the crop burning region before arriving at the receptor location in New Delhi; this further corroborates the transport patterns inferred from the satellite data. A 15-year long satellite record (2002-2016) reveals an increasing trend in agricultural fires (~617 per year) and aerosol loading (0.031 and 0.04 per year in aerosol optical depth and UV aerosol index) in November. Increasing levels of crop residue burning and resulting particulate matter pollution at an alarming rate over northern India is a pressing concern demanding corrective measures to substantially reduce or completely diminish the crop burning through an effective residue management system.

Crop Residue Fires↗
DOE OSTI2017

Ortho-para interconversion in cation-water complexes: The case of V + (H 2 O) and Nb + (H 2 O) clusters

Vanadium and niobium cation-water complexes, V + (H 2 O) and Nb + (H 2 O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O–H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. We report the $A$ rotational constants are smaller than expected and the normal 1:3 intensity ratios for K = even:odd levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted Multi-Reference Configuration Interaction (icMRCI) and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to quasi-C 2v symmetry with significant probability off the C 2 axis, thus explaining the reduced $A$ values. Both vanadium and iobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 sec-1).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗