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

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All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of <150 micron fines from ten sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform (RN) and drilled Sheepbed mudstone from sites John Klein (JK) and Cumberland (CB). One was drilled from the Windjana (WJ) site on a sandstone of the Kimberly formation. Four were drilled from sites Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP) and Buckskin (BK) of the Murray Formation at the base of Mt. Sharp. Two were drilled from sandstones of the Stimson formation targeting relatively unaltered (Big Sky, BY) and then altered (Greenhorn, GH) material associated with a light colored fracture zone. CheMin analyses provided quantitative sample mineralogy. SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases. This contribution will focus on evolved SO2. All samples evolved SO2 above 500 C. The shapes of the SO2 evolution traces with temperature vary between samples but most have at least two "peaks' within the wide high temperature evolution, from approx. 500-700 and approx. 700-860 C (Fig. 1). In many cases, the only sulfur minerals detected with CheMin were Ca sulfates (e.g., RN and GH), which should thermally decompose at temperatures above those obtainable by SAM (>860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

McAdam, A. C.↗
NASA NTRS2016

A Laser-Induced Fluorescence Instrument for Aircraft Measurements of Sulfur Dioxide in the Upper Troposphere and Lower Stratosphere

This work describes the development and testing of a new instrument for in situ measurements of sulfur dioxide (SO2) on airborne platforms in the upper troposphere and lower stratosphere (UTLS). The instrument is based on the laser-induced fluorescence technique and uses the fifth harmonic of a tunable fiber-amplified semiconductor diode laser system at 1084.5 nm to excite SO2 at 216.9 nm. Sensitivity and background checks are achieved in flight by additions of SO2 calibration gas and zero air, respectively. Aircraft demonstration was performed during the NASA Volcano Plume Investigation Readiness and Gas-Phase and Aerosol Sulfur (VIRGAS) experiment, which was a series of flights using the NASA WB-57F during October 2015 based at Ellington Field and Harlingen, Texas. During these flights, the instrument successfully measured SO2 in the UTLS at background (non-volcanic) conditions with a precision of 2 ppt at 10 s and an overall uncertainty determined primarily by instrument drifts of +/- (16% + 0.9 ppt).

tunable fiber-amplified semiconductor diode laser ↗
DOE OSTI2026

Liquified SO 2 induced solid/cathode electrolyte interphase for lithium ion batteries

Formation of robust solid/cathode electrolyte interphases (S/CEI) is vital for long-term stability and high-performance operation of lithium-ion batteries (LIBs), particularly under high voltage regimes. However, engineering electrochemically stable S/CEIs that effectively suppress interfacial side reactions remains a key challenge. Herein, we introduce a liquefied sulfur dioxide (SO 2 )– ionic liquid complex as a fluorine-free multifunctional electrolyte additive for the first time that significantly improves the formation of sulfate/sulfite-rich S/CEI layers at both graphite and NMC811 interfaces. The unique SO 2 -N coordination with a 1,2,4-triazolide-based ionic liquid enables homogeneous SO 2 dissolution, resulting in controlled SO 2 decomposition during the initial electrochemical cycle. This decomposition yields sulfur-rich interphase species that stabilize the electrolyte-electrode interface, reduce impedance growth, and lessen electrolyte decomposition. Electrochemical tests show significantly improved cycle life, reduced polarization, and increased Coulombic efficiency for both anodes and cathodes. XPS confirms the presence of SO 2 -derived surface species that contribute to interfacial stability. In conclusion, this approach highlights a new direction for interphase engineering using liquefied gas additives and opens pathways for sulfur-based S/CEI chemistry in advanced battery systems.

Graphite↗
NASA NTRS1987

Computer simulation of thermal modeling of primary lithium cells

The objective was to gain a better understanding of the safety problem of primary Li-SOCl2 and Li-SO2 cells by carrying out detailed thermal modeling work. In particular, the transient heat generation rates during moderate and extermely high discharge rate tests of Li-SOCl2 cells were predicted and compared with those from the electrochemical heating. The difference between the two may be attributed to the lithium corrosion and other chemical reactions. The present program was also tested for charging of Li-SO2. In addition, the present methodology should be applicable to other primary cylindrical cells as well as rechargeable battery analyses with minor modifications.

Young, I. Cho↗
NASA NTRS1995

MODTRAN3: An update and recent validations against airborne high resolution interferometer measurements

MODTRAN, the Moderate Resolution Atmospheric Radiance and Transmittance Model, encompasses all the capabilities of LOWTRAN 7, the widely used 20 cm(exp -1) resolution radiance code, but incorporates a much more sensitive molecular band model with 2 cm(exp -1) resolution. MODTRAN contains many important elements that other band model based radiative transfer codes do not incorporate. It shares with FASCODE: spherical geometry, single and multiple scattering default atmospheric profile descriptors (gases, aerosols, clouds, fogs, and rain), and molecular continua (H2O, CO2, O3, O2, N2). In addition, it can calculate the solar/lunar direct and scattered radiation. MODTRAN3 was released to the general public in November 1994. It has several important features that the previous version, MODTRAN2, does not have. Chloro-fluorocarbon (CFC) and related heavy molecules (whose spectroscopic properties first appear on the HITRAN92 data base as temperature-dependent cross sections) have been incorporated into pseudo-band models, with provision for using both default and user supplied profiles. The addition of SO2 and O2 in the UV, along with upgraded ozone Chappuis bands in the visible is also part of MODTRAN3. An improved multiple scattering algorithm, the DIScrete Ordinate Radiative Transfer (DISORT) has also been incorporated into MODTRAN3. MODTRAN is very fast: simple timing runs of MODTRAN3 vs. FASCOD3 show an improvement of more than a factor of 100 for a typical 500 cm(exp -1) spectral interval and comparable vertical layering. Speed is an important consideration in heating/cooling rates calculations, where a large number of radiative transfer calculations are needed. The MODTRAN3 used in this study is based on HITRAN92, but as mentioned, above, it will be upgraded to HITRAN94 upon its release at the end of 1994. MODTRAN has been adopted by: some researchers in the AVIRIS program as one radiative transfer code to derive surface reflectance from AVIRIS measurements. The accuracy of the code is very important because any errors in the radiative transfer calculation will directly translate into errors in the derived surface reflectance. In this paper, the new solar irradiance calculated by Kurucz, which is adopted in MODTRAN3, will be presented. Recent validations of MODTRAN3 with airborne high resolution interferometer measurements over ocean will be discussed. Good agreeement between model calculations and measurements was achieved.

Anderson, Gail P.↗
NASA NTRS2002

Theoretical Study of Infrared and Raman Spectra of Hydrated Magnesium Sulfate Salts

Harmonic and anharmonic vibrational frequencies, as well as infrared and Raman intensities, are calculated for MgSO4.nH20 (n=1-3). Electronic structure theory at the second order Moller-Plesset perturbation theory (MP2) level with a triple-zeta + polarization (TZP) basis set is used to determine the geometry, properties, and vibrational spectra of pure and hydrated MgSO4 salts. The direct vibrational self-consistent field (VSCF) method and its correlation corrected (CC-VSCF) extension are used to determine anharmonic corrections to vibrational frequencies and intensities for the pure MgSO4 and its complex with one water molecule. Very significant differences are found between vibrational of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies are shifted to the red very significantly (by up to 1500-2000/cm) upon complexation with magnesium sulfate. They should be observed between 1700 and 3000/cm in a region very different from the corresponding O-H stretch frequency region of pure water (3700-3800/cm). In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. They can serve as unique identifiers for the presence of sulfate salts. The predicted infrared and Raman spectra should be of valuable help in the design of future missions and analysis of observed data from the ice surface of Jupiter's moon Europa that possibly contains hydrated MgSO4 salts.

Chaban, Galina M.↗
NASA NTRS2002

Infrared Spectra of Hydrated Magnesium Salts and their Role in the Search for Possible Life Conditions on Jupiter Moons

Recent observations from the Galileo satellite indicate that three of the Jupiter moons, Europa, Ganymede, and Callisto, may have subsurface oceans. Possible existence of such ocean and the nature of its composition are of great interest to astrobiologists. Data from Galileo's NIMS spectrometer indicate the possibility of hydrated salts on Europa's surface. To aid in the design of future missions, we investigated infrared spectra of MgSO4-nH20, n=1-3 using ab initio calculations. Geometry, energetics, dipole moments, vibrational frequencies and infrared intensities of pure and hydrated MgSO4 salts were determined. Significant differences are found between vibrational spectra of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies in the complexes are shifted to the red by up to 1,500 - 2,000 per cm. In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. The calculated bands of water and SO2 fragments can serve as markers for the existence of the salt-water complexes on the surface of Jupiter's moon.

Chaban, Galina↗
NASA NTRS2022

Limitations in Representation of Physical Processes Prevents Successful Simulation of PM2.5 During KORUS-AQ

High levels of fine particulate matter (PM2.5) pollution in East Asia often exceed local air quality standards. Observations from the Korea United States-Air Quality (KORUS-AQ) field campaign in May and June 2016 showed that development of extreme pollution (haze) occurred through a combination of long-range transport and favorable meteorological conditions that enhanced local production of PM2.5. Atmospheric models often have difficulty simulating PM2.5 chemical composition during haze, which is of concern for the development of successful control measures. We use observations from KORUS-AQ to examine the ability of the GEOS-Chem chemical transport model to simulate PM2.5 composition throughout the campaign and identify the mechanisms driving the pollution event. At the surface, the model underestimates sulfate by -64% but overestimates nitrate by +36%. The largest underestimate in sulfate occurs during the pollution event, where models typically struggle to generate elevated sulfate concentrations due to missing heterogeneous chemistry in aerosol liquid water in the polluted boundary layer. Hourly surface observations show that the model nitrate bias is driven by an overestimation of the nighttime peak. In the model, nitrate formation is limited by the supply of nitric acid, which is biased by +100% against aircraft observations. We hypothesize that this is due to a large missing sink, which we implement here as a factor of five increase in dry deposition. We show that the resulting increased deposition velocity is consistent with observations of total nitrate as a function of photochemical age. The model does not account for factors such as the urban heat island effect or the heterogeneity of the built-up urban landscape resulting in insufficient model turbulence and surface area over the study area that likely results in insufficient dry deposition. Other species such as NH3 could be similarly affected but were not measured during the campaign. Nighttime production of nitrate is driven by NO2 hydrolysis in the model, while observations show that unexpectedly elevated nighttime ozone (not present in the model) should result in N2O5 hydrolysis as the primary pathway. The model is unable to represent nighttime ozone due to an overly rapid collapse of the afternoon mixed layer and excessive titration by NO. We attribute this to missing nighttime heating driving deeper nocturnal mixing that would be expected to occur in a city like Seoul. This urban heating is not considered in air quality models run at large enough scales to treat both local chemistry and long-range transport. Key model failures in simulating nitrate, mainly overestimated daytime nitric acid, incorrect representation of nighttime chemistry, and an overly shallow and insufficiently turbulent nighttime mixed layer, exacerbate the model’s inability to simulate the buildup of PM2.5 during haze pollution. To address the underestimate in sulfate most evident during the haze event, heterogeneous aerosol uptake of SO2 is added to the model which previously only considered aqueous production of sulfate from SO2 in cloud water. Implementing a simple parameterization of this chemistry improves the model abundance of sulfate but degrades the SO2 simulation implying that emissions are underestimated. We find that improving model simulations of sulfate has direct relevance to determining local vs. transboundary contributions to PM2.5. During the haze pollution event, the inclusion of heterogeneous aerosol uptake of SO2 decreases the fraction of PM2.5 attributable to long-range transport from 66% to 54%. Locally-produced sulfate increased from 1% to 25% of locally-produced PM2.5, implying that local emissions controls would have a larger effect than previously thought. However, this additional uptake of SO2 is coupled to the model nitrate prediction which affects the aerosol liquid water abundance and chemistry driving sulfate-nitrate-ammonium partitioning. An additional simulation of the haze pollution with heterogeneous uptake of SO2 to aerosol and simple improvements to the model nitrate simulation results in 30% less sulfate due to 40% less nitrate and aerosol water, and results in an underestimate of sulfate during the haze event. Future studies need to better consider the impact of model physical processes such as dry deposition and nighttime boundary layer mixing on the simulation of nitrate and the effect of improved nitrate simulations on the overall simulation of secondary inorganic aerosol (sulfate+nitrate+ammonium) in East Asia. Foreign emissions are rapidly changing, increasing the need to understand the impact of local emissions on PM2.5 in South Korea to ensure continued air quality improvements.

Katherine R. Travis↗
NASA NTRS1997

A 2D Microphysical Analysis of Aerosol Nucleation in the Polar Winter Stratosphere: Implications for H2SO4 Photolysis and Nucleation Mechanisms

Each spring a layer of small particles forms between 20 and 30 km in the polar regions. Results are presented from a 2D microphysical model of sulfate aerosol, which provide the first self-consistent explanation of the observed "CN layer." Photochemical conversion of sulfuric acid to SO2 in the upper stratosphere and mesosphere is necessary for this layer to form. Recent laboratory measurements of H2SO4 and SO3 photolysis rates are consistent with such conversion, though an additional source of SO2 may be required. Nucleation throughout the polar winter extends the top of the aerosol layer to higher altitudes, despite strong downward transport of ambient air. This finding may be important to heterogeneous chemistry at the top of the aerosol layer in polar winter and spring.

Mills, Michael J.↗
NASA NTRS2010

Direct Retrieval of Sulfur Dioxide Amount and Altitude from Spaceborne Hyperspectral UV Measurements: Theory and Application

We describe the physical processes by which a vertically localized absorber perturbs the top-of-atmosphere solar backscattered ultraviolet (UV) radiance. The distinct spectral responses to perturbations of an absorber in its column amount and layer altitude provide the basis for a practical satellite retrieval technique, the Extended Iterative Spectral Fitting (EISF) algorithm, for the simultaneous retrieval of these quantities of a SO2 plume. In addition, the EISF retrieval provides an improved UV aerosol index for quantifying the spectral contrast of apparent scene reflectance at the bottom of atmosphere bounded by the surface and/or cloud; hence it can be used for detection of the presence or absence of UV absorbing aerosols. We study the performance and characterize the uncertainties of the EISF algorithm using synthetic backscattered UV radiances, retrievals from which can be compared with those used in the simulation. Our findings indicate that the presence of aerosols (both absorbing and nonabsorbing) does not cause large errors in EISF retrievals under most observing conditions when they are located below the SO2 plume. The EISF retrievals assuming a homogeneous field of view can provide accurate column amounts for inhomogeneous scenes, but they always underestimate the plume altitudes. The EISF algorithm reduces systematic errors present in existing linear retrieval algorithms that use prescribed SO2 plume heights. Applying the EISF algorithm to Ozone Monitoring Instrument satellite observations of the recent Kasatochi volcanic eruption, we demonstrate the successful retrieval of effective plume altitude of volcanic SO2, and we also show the improvement in accuracy in the corresponding SO2 columns.

Yang, Kau↗
NASA NTRS1982

Radiative effects of the El Chichon volcanic eruption. Preliminary results concerning remote sensing

The aerosols and gases resulting from the El Chichon volcanic eruption had, and may still have, significant effects on satellite measurements of the properties of the Earth's atmosphere. The sea surface temperature measured by the AVHRR was biased up to -2.5 C for many months. The total amount of ozone derived from TOMS with a standard algorithm was greatly in excess of the possible value. This apparent excess can now be explained in terms of additional absorption by SO2. Infrared temperature sounders have observed both positive and negative anomalies. These effects and others on many satellite measurements are addressed following a discussion of the history and composition of the ejecta remaining in the stratosphere. Finally, recommendations are made for further study to account for the effects of volcanic eruptions on satellite observations and for use of such observations to measure the characteristics of the ejecta.

Bandeen, W. R.↗
NASA NTRS2017

Incorporating Planetary-Scale Waves Into the VTGCM: Understanding the Waves Impact on the Upper Atmosphere of Venus.

Venus has proven to have a very dynamic upper atmosphere. The upper atmosphere of Venus has been observed for many decades by multiple means of observation (e.g. ground-based, orbiters, probes, fly-by missions going to other planets). As of late, the European Space Agency Venus Express (VEX) orbiter has been a main observer of the Venusian atmosphere. Specifically, observations of Venus' O2 IR nightglow emission have been presented to show its variability. Nightglow emission is directly connected to Venus' circulation and is utilized as a tracer for the atmospheric global wind system. More recent observations are adding and augmenting temperature and density (e.g. CO, CO2, SO2) datasets. These additional datasets provide a means to begin analyzing the variability and study the potential drivers of the variability. A commonly discussed driver of variability is wave deposition. Evidence of waves has been observed, but these waves have not been completely analyzed to understand how and where they are important. A way to interpret the observations and test potential drivers is by utilizing numerical models.

Venus↗
NASA NTRS1997

CO2 greenhouse in the early martian atmosphere: SO2 inhibits condensation

Many investigators of the early martian climate have suggested that a dense carbon dioxide atmosphere was present and warmed the surface above the melting point of water (J.B. Pollack, J.F. Kasting, S.M. Richardson, and K. Poliakoff 1987. Icarus 71, 203-224). However, J.F. Kasting (1991. Icarus 94, 1-13) pointed out that previous thermal models of the primitive martian atmosphere had not considered the condensation of CO2. When this effect was incorporated, Kasting found that CO2 by itself is inadequate to warm the surface. SO2 absorbs strongly in the near UV region of the solar spectrum. While a small amount of SO2 may have a negligible effect by itself on the surface temperature, it may have significantly warmed the middle atmosphere of early Mars, much as ozone warms the terrestrial stratosphere today. If this region is kept warm enough to inhibit the condensation of CO2, then CO2 remains a viable greenhouse gas. Our preliminary radiative modeling shows that the addition of 0.1 ppmv of SO2 in a 2 bar CO2 atmosphere raises the temperature of the middle atmosphere by approximately 10 degrees, so that the upper atmosphere in a 1 D model remains above the condensation temperature of CO2. In addition, this amount of SO2 in the atmosphere provides an effective UV shield for a hypothetical biosphere on the martian surface.

NASA Discipline Exobiology↗
NASA NTRS1977

Influence of ground level SO2 on the diffuse to direct irradiance ratio in the middle ultraviolet

The dependence of the ratio of the diffuse to direct irradiances at the ground were examined for a wavelength of 315.1 nm. A passive remote sensing method based on ratio measurements for obtaining the optical thickness of SO2 in the vertical column was proposed. If, in addition to the ratio measurements, the SO2 density at the ground is determining using an appropriate point-sampling technique then some inference on the vertical extent of SO2 can be drawn. An analytic representation is presented of the ratio for a wide range of SO2 and aerosol optical thicknesses and solar zenith angles which can be inverted algebraically to give the SO2 optical thickness in terms of the measured ratio, aerosol optical thickness and solar zenith angle.

Klenk, K. F.↗
NASA NTRS1987

Thermodynamic state of SO2 on Io's surface

It has been suggested that surface conditions on Io might be conducive to significant SO2 adsorption on sulfur or alkali sulfides. A number of spectroscopic arguments for and against the high abundance of a SO2 adsorbate (versus frost) on Io have been made. SO2 absorption isotherms on particulate sulfur are measured, and the question of SO2 adsorbate/ice is approached from a thermodynamic perspective. Because of formidable experimental difficulties, data were not obtained at the very low temperatures and P(SO2) characteristics of Io; however, data were obtained over a wide range of pressures and temperatures somewhat higher than Io's and extrapolated to Io surface conditions. Errors in estimating adsorptive capacity accrue through extrapolation of the adsorption isotherms; however, more significant is the addition of the solid SO2 equilibrium vapor pressure curve to the phase diagram. The formation of ice places a strict upper limit on adsorptive coverage at any temperature. The limit for Io based upon the data is calculated, and it is shown that no more than 0.014 monolayers of SO2 can adsorb on sulfur at Io temperatures. Given the assumption that sulfur forms the primary adsorbent on Io's surface, or the assumption that the adsorptive capacity of the other adsorbents is not substantially greater than that of sulfur, this explains the fact that the nu(1) + nu(3) band center position is in better agreement with that of frost than adsorbate.

Zent, Aaron P.↗
NASA NTRS1979

Sulfur dioxide in the Venus atmosphere - Distribution and implications

The Pioneer Venus Orbiter ultraviolet spectrometer sees variable disk brightness features similar to the well-known 'UV markings' seen at longer wavelengths. The bright features are consistent with a homogeneous cloud of H2SO4 aerosols. The darker features show the presence of a broad-band absorber, which is at some depth in the cloud layer. Additional contrast arises from SO2 absorption. The observed strength of the SO2 absorption as a function of wavelength rules out a uniform mixing ratio for the SO2. The data are well fitted by an inhomogeneous light scattering model in which the SO2 scale height is one-fifth of the CO2 scale height, and the mixing ratio of SO2 at 40 mb is 10 to the -7th. A model of the oxidation of sulfur dioxide in the upper cloud reproduces the observed vertical distribution of SO2 and indicates that SO2 alone is sufficient to produce the observed amount of H2SO4 in this region.

Esposito, L. W.↗
NASA NTRS2001

HST/STIS Visible Images of Io in Eclipse

On 1999 August 27, Io was observed with HST STIS/CCD using a 2"x 2" aperture soon after it entered into eclipse (CML = 342 to 346). Two G750M/I spectral images, covering 5815 Angstroms to 6380 Angstroms and starting 3 and 17 minutes after 2nd contact, recorded emissions of Na I 5890,5896 Angstroms and [O I] 6300,6364 Angstroms. The oxygen and sodium emissions show several similar features. (1) Downstream wake emission that correlates in location with jovian magnetic field orientation; (2) Enhanced emissions near the sub-jovian region, albeit a relatively weak enhancement for sodium; and (3) Limb glow that is brighter in the hemisphere facing the jovian magnetic equator. These features are qualitatively similar to [O I] 6300 Angstrom images obtained with HST WFPC2 and to the UV STIS results of Roesler et al. 1999 (Science, 283, 353), as well as broadband images taken by the Galileo SSI (Geissler et al. JGR submitted) and more recent Cassini images. The integrated oxygen (6300 Angstrom + 6364 Angstrom) emission intensity (10.5 k Rayleighs (kR) disk averaged) did not change between the two exposures while the integrated disk averaged sodium D emission intensity decreased by 19% from 5.7 kR to 4.6 kR. Also, in contrast to the oxygen emission, sodium showed relatively enhanced emission in the northern polar regions. Likewise, on 1999 August 23, Io eclipse STIS observations were made in the near-UV and blue regions to try to identify the Galileo SSI violet filter emissions. Preliminary analysis reveals a residual signal after subtraction of a dominant scattered light background that is suggestive of a SO2 band structure. In addition, the largest individual emission at about 4075 Angstrom could be the S(+) doublet.

Oliversen, Ron J.↗
NASA NTRS1998

Atomization Energies of SO and SO2; Basis Set Extrapolation Revisted

The addition of tight functions to sulphur and extrapolation to the complete basis set limit are required to obtain accurate atomization energies. Six different extrapolation procedures are tried. The best atomization energies come from the series of basis sets that yield the most consistent results for all extrapolation techniques. In the variable alpha approach, alpha values larger than 4.5 or smaller than 3, appear to suggest that the extrapolation may not be reliable. It does not appear possible to determine a reliable basis set series using only the triple and quadruple zeta based sets. The scalar relativistic effects reduce the atomization of SO and SO2 by 0.34 and 0.81 kcal/mol, respectively, and clearly must be accounted for if a highly accurate atomization energy is to be computed. The magnitude of the core-valence (CV) contribution to the atomization is affected by missing diffuse valence functions. The CV contribution is much more stable if basis set superposition errors are accounted for. A similar study of SF, SF(+), and SF6 shows that the best family of basis sets varies with the nature of the S bonding.

Bauschlicher, Charles W., Jr.↗