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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Quality correction factors of composite IMRT beam deliveries: Theoretical considerations

Purpose: In the scope of intensity modulated radiation therapy (IMRT) dosimetry using ionization chambers, quality correction factors of plan-class-specific reference (PCSR) fields are theoretically investigated. The symmetry of the problem is studied to provide recommendable criteria for composite beam deliveries where correction factors are minimal and also to establish a theoretical limit for PCSR delivery k{sub Q} factors. Methods: The concept of virtual symmetric collapsed (VSC) beam, being associated to a given modulated composite delivery, is defined in the scope of this investigation. Under symmetrical measurement conditions, any composite delivery has the property of having a k{sub Q} factor identical to its associated VSC beam. Using this concept of VSC, a fundamental property of IMRT k{sub Q} factors is demonstrated in the form of a theorem. The sensitivity to the conditions required by the theorem is thoroughly examined. Results: The theorem states that if a composite modulated beam delivery produces a uniform dose distribution in a volume V{sub cyl} which is symmetric with the cylindrical delivery and all beams fulfills two conditions in V{sub cyl}: (1) the dose modulation function is unchanged along the beam axis, and (2) the dose gradient in the beam direction is constant for a given lateral position; then its associated VSC beam produces no lateral dose gradient in V{sub cyl}, no matter what beam modulation or gantry angles are being used. The examination of the conditions required by the theorem lead to the following results. The effect of the depth-dose gradient not being perfectly constant with depth on the VSC beam lateral dose gradient is found negligible. The effect of the dose modulation function being degraded with depth on the VSC beam lateral dose gradient is found to be only related to scatter and beam hardening, as the theorem holds also for diverging beams. Conclusions: The use of the symmetry of the problem in the present paper leads to a valuable theorem showing that k{sub Q} factors of composite IMRT beam deliveries are close to unity under specific conditions. The theoretical limit k{sub Q{sub p{sub c{sub s{sub r,Q{sub m{sub s{sub r}{sup f{sub p}{sub c}{sub s}{sub r},f{sub m}{sub s}{sub r}}}}}}}}}=1 is determined based on the property of PCSR deliveries to provide a uniform dose in the target volume. The present approach explains recent experimental observations and proposes ideal conditions for IMRT reference dosimetry. The result of this study could potentially serve as a theoretical basis for reference dosimetry of composite IMRT beam deliveries or for routine IMRT quality assurance.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

Microwave plasma source operating with atmospheric pressure air-water mixtures

The overall performance of a surface wave driven air-water plasma source operating at atmospheric pressure and 2.45 GHz has been analyzed. A 1D model previously developed has been improved in order to describe in detail the creation and loss processes of active species of interest. This model provides a complete characterization of the axial structure of the source, including the discharge and the afterglow zones. The main electron creation channel was found to be the associative ionization process N + O {yields} NO{sup +}+ e. The NO(X) relative density in the afterglow plasma jet ranges from 1.2% to 1.6% depending on power and water percentage, according to the model predictions and the measurements. Other types of species such as NO{sub 2} and nitrous acid HNO{sub 2} have also been detected by mass and Fourier Transform Infrared spectroscopy. The relative population density of O({sup 3}P) ground state atoms increases from 8% to 10% in the discharge zone when the input microwave power increases from 200 to 400 W and the water percentage from 1% to 10%. Furthermore, high densities of O{sub 2}(a{sup 1}{Delta}{sub g}) singlet delta oxygen molecules and OH radicals (1% and 5%, respectively) can be achieved in the discharge zone. In the late afterglow the O{sub 2}(a{sup 1}{Delta}{sub g}) density is about 0.1% of the total density. This plasma source has a flexible operation and potential for channeling the energy in ways that maximize the density of active species of interest.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Conformer-Specific Dissociation Dynamics in Dimethyl Methylphosphonate Radical Cation

The dynamics of the dimethyl methylphosphonate (DMMP) radical cation after production by strong field adiabatic ionization have been investigated. Pump-probe experiments using strong field 1300 nm pulses to adiabatically ionize DMMP and a 800 nm non-ionizing probe induce coherent oscillations of the parent ion yield with a period of about 45 fs. The yields of two fragments, PO 2 C 2 H 7 + and PO 2 CH 4 + , oscillate approximately out of phase with the parent ion, but with a slight phase shift relative to each other. We use electronic structure theory and nonadiabatic surface hopping dynamics to understand the underlying dynamics. The results show that while the cation oscillates on the ground state along the P=O bond stretch coordinate, the probe excites population to higher electronic states that can lead to fragments PO 2 C 2 H 7 + and PO 2 CH 4 + . The computational results combined with the experimental observations indicate that the two conformers of DMMP that are populated under experimental conditions exhibit different dynamics after being excited to the higher electronic states of the cation leading to different dissociation products. These results highlight the potential usefulness of these pump-probe measurements as a tool to study conformer-specific dynamics in molecules of biological interest.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Benchmarking boron carbide equation of state using computation and experiment

Boron carbide ( B 4 C ) is of both fundamental scientific and practical interest due to its structural complexity and how it changes upon compression, as well as its many industrial uses and potential for use in inertial confinement fusion (ICF) and high-energy density physics experiments. Here, we report the results of a comprehensive computational study of the equation of state (EOS) of B 4 C in the liquid, warm dense matter, and plasma phases. Our calculations are cross-validated by comparisons with Hugoniot measurements up to 61 megabar from planar shock experiments performed at the National Ignition Facility (NIF). Our computational methods include path integral Monte Carlo, activity expansion, as well as all-electron Green's function Korringa-Kohn-Rostoker and molecular dynamics that are both based on density functional theory. We calculate the pressure-internal energy EOS of B 4 C over a broad range of temperatures ( ~ 6 × 10 3 – 5 × 10 8 K) and densities (0.025–50 g / cm 3 ). We assess that the largest discrepancies between theoretical predictions are ≲ 5 % near the compression maximum at 1– 2 × 10 6 K. This is the warm-dense state in which the K shell significantly ionizes and has posed grand challenges to theory and experiment. By comparing with different EOS models, we find a Purgatorio model (LEOS 2122) that agrees with our calculations. The maximum discrepancies in pressure between our first-principles predictions and LEOS 2122 are ~ 18 % and occur at temperatures between 6 × 10 3 – 2 × 10 5 K, which we believe originate from differences in the ion thermal term and the cold curve that are modeled in LEOS 2122 in comparison with our first-principles calculations. To account for potential differences in the ion thermal term, we have developed three new equation-of-state models that are consistent with theoretical calculations and experiment. We apply these new models to 1D hydrodynamic simulations of a polar direct-drive NIF implosion, demonstrating that these new models are now available for future ICF design studies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Three-Dimensional Imaging of Lipids and Metabolites in Tissues by Nanospray Desorption Electrospray Ionization Mass Spectrometry

Abstract Three-dimensional (3D) imaging of tissue sections is a new frontier in mass spectrometry imaging (MSI). Here we report on fast 3D imaging of lipids and metabolites associated with mouse uterine decidual cells and embryo at the implantation site on day 6 of pregnancy. 2D imaging of 16-20 serial tissue sections deposited on the same glass slide was performed using nanospray desorption electrospray ionization (nano-DESI) – an ambient ionization technique that enables sensitive localized analysis of analytes on surfaces without special sample pre-treatment. In this proof-of-principle study, nano-DESI was coupled to a high-resolution Q-Exactive instrument operated at high repetition rate of >5 Hz with moderate mass resolution of 35,000 (m/Δm at m/z 200), which enabled acquisition of the entire 3D image with a spatial resolution of ~150 μm in less than 4.5 hours. The results demonstrate localization of acetylcholine in the primary decidual zone (PDZ) of the implantation site throughout the depth of the tissue examined, indicating an important role of this signaling molecule in decidualization. Choline and phosphocholine – metabolites associated with cell growth – are enhanced in the PDZ and abundant in other cellular regions of the implantation site. Very different 3D distributions were obtained for fatty acids (FA), oleic acid and linoleic acid (FA 18:1 and FA 18:2), differing only by one double bond. Localization of FA 18:2 in the PDZ indicates its important role in decidualization while FA 18:1 is distributed more evenly throughout the tissue. In contrast, several lysophosphatidylcholines (LPC) observed in this study show donut-like distributions with localization around the PDZ. Complementary distributions with minimal overlap were observed for LPC 18:0 and FA 18:2 while the 3D image of the potential precursor phosphatidylcholine (PC 36:2) showed a significant overlap with both LPC 18:0 and FA 18:2.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2016

The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory

This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other properties such as geometries, reaction barrier heights, and atomization energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reevaluation of Radiation-Protection Standards for Workers and the Public Based on Current Scientific Evidence

President Trump’s recent executive orders to “Usher in a Nuclear Renaissance,” coupled with the global pledge to triple nuclear energy capacity by 2050, underscore nuclear energy’s importance to national security and economic prosperity. This renewed interest has prompted efforts to spur nuclear-energy deployment, including assessing factors impeding it. One issue that has previously been identified as adding to the cost of nuclear energy is excessively conservative requirements, including those related to radiation protection. This technical review, therefore, examines current radiation-protection standards that were established decades ago when more limited data were available and nuclear-energy expansion was not a national priority. The review focuses on scientific evidence regarding the health effects of ionizing radiation at annual doses of 10,000 mrem or less. The review evaluates epidemiological studies, radiobiological research, and positions of relevant professional organizations to assess whether such doses result in discernable or observable increases in negative health outcomes. The review also surveys the literature related to economic and practical implications of current radiation-protection standards and practices. Based on this assessment, we propose maintaining an annual occupational whole-body dose limit of 5,000 mrem/yr and eliminating all “as low as reasonably achievable” requirements and limits below this threshold. This change could potentially reduce radiation-protection costs by millions of dollars annually for each reactor, as well as decrease the overall costs and correct misconceptions about the risks associated with all nuclear technologies. The evidence further supports future consideration of a 10,000 mrem/yr limit that would maintain appropriate safety margins while further reducing protection costs. Similarly, given the data and that the average annual radiation dose per person in the U.S. is 620 mrem, we believe the public dose limits of 100 mrem/yr are unnecessarily restrictive; increasing to 500 mrem/yr would maintain substantial safety margins—a factor of 10 below the occupational limit—while reducing regulatory burdens and associated bureaucracy. While we acknowledge ongoing scientific debate and encourage continued research on the health effects of ionizing radiation, our review indicates current frameworks are overly conservative. These overly stringent limits not only impose unnecessary economic burdens without corresponding health benefits but also divert safety focus and resources from more important considerations. Although this study was motivated by nuclear-power considerations, reforms to radiation-protection requirements have significant positive implications for other areas, such as nuclear medical applications, environmental remediation, nuclear-waste management and disposal, and industrial applications of nuclear technologies.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2023

Defect physics in 2D monolayer I-VII semiconductor AgI

As a brand new two-dimensional (2D) material with promising electronic properties, monolayer I-VII silver iodide (AgI) has the potential for future 2D electronic devices. To advance the development of such devices, the exploration of n-type and p-type conductivities of AgI is indispensable. With first-principles calculations, we systematically investigate the properties of intrinsic defects and extrinsic dopants in monolayer AgI, including atomic structural pictures, formation energies, and ionization energies to offer carriers. Considering the divergence in energies of charged defects in 2D materials when the traditional jellium scheme is used, we adopt an extrapolation approach to overcome the problem. The Ag vacancy (VAg) and Be substitution on Ag site (BeAg) are found to be the most promising p-type and n-type doping candidates, respectively. They could provide bound carriers for transport through the defect-bound band edge states, although the ionization energies are still larger than thermal energy at room temperature. Furthermore, negative-U behaviors are demonstrated in I vacancy (VI), Zn substitution on Ag site (ZnAg), and Cd substitution on Ag site (CdAg). The present work, for the first time, offers a detailed study of the defect physics in 2D I-VII monolayer semiconductor, laying the foundation for subsequent physics and device explorations based on these brand new 2D materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Unipolar resistive switching in metal oxide/organic semiconductor non-volatile memories as a critical phenomenon

Diodes incorporating a bilayer of an organic semiconductor and a wide bandgap metal oxide can show unipolar, non-volatile memory behavior after electroforming. The prolonged bias voltage stress induces defects in the metal oxide with an areal density exceeding 10{sup 17 }m{sup −2}. We explain the electrical bistability by the coexistence of two thermodynamically stable phases at the interface between an organic semiconductor and metal oxide. One phase contains mainly ionized defects and has a low work function, while the other phase has mainly neutral defects and a high work function. In the diodes, domains of the phase with a low work function constitute current filaments. The phase composition and critical temperature are derived from a 2D Ising model as a function of chemical potential. The model predicts filamentary conduction exhibiting a negative differential resistance and nonvolatile memory behavior. The model is expected to be generally applicable to any bilayer system that shows unipolar resistive switching.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Excited state dynamics of cis , cis -1,3-cyclooctadiene: UV pump VUV probe time-resolved photoelectron spectroscopy

We present UV pump, vacuum ultraviolet probe time-resolved photoelectron spectroscopy measurements of the excited state dynamics of cis,cis-1,3-cyclooctadiene. A 4.75 eV deep UV pump pulse launches a vibrational wave packet on the first electronically excited state, and the ensuing dynamics are probed via ionization using a 7.92 eV probe pulse. The experimental results indicate that the wave packet undergoes rapid internal conversion to the ground state in under 100 fs. Comparing the measurements with electronic structure and trajectory surface hopping calculations, we are able to interpret the features in the measured photoelectron spectra in terms of ionization to several states of the molecular cation.

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

SU-E-T-257: Output Constancy: Reducing Measurement Variations in a Large Practice Group

Purpose: To standardize output constancy check procedures in a large medical physics practice group covering multiple sites, in order to identify and reduce small systematic errors caused by differences in equipment and the procedures of multiple physicists. Methods: A standardized machine output constancy check for both photons and electrons was instituted within the practice group in 2010. After conducting annual TG-51 measurements in water and adjusting the linac to deliver 1.00 cGy/MU at Dmax, an acrylic phantom (comparable at all sites) and PTW farmer ion chamber are used to obtain monthly output constancy reference readings. From the collected charge reading, measurements of air pressure and temperature, and chamber Ndw and Pelec, a value we call the Kacrylic factor is determined, relating the chamber reading in acrylic to the dose in water with standard set-up conditions. This procedure easily allows for multiple equipment combinations to be used at any site. The Kacrylic factors and output results from all sites and machines are logged monthly in a central database and used to monitor trends in calibration and output. Results: The practice group consists of 19 sites, currently with 34 Varian and 8 Elekta linacs (24 Varian and 5 Elekta linacs in 2010). Over the past three years, the standard deviation of Kacrylic factors measured on all machines decreased by 20% for photons and high energy electrons as systematic errors were found and reduced. Low energy electrons showed very little change in the distribution of Kacrylic values. Small errors in linac beam data were found by investigating outlier Kacrylic values. Conclusion: While the use of acrylic phantoms introduces an additional source of error through small differences in depth and effective depth, the new standardized procedure eliminates potential sources of error from using many different phantoms and results in more consistent output constancy measurements.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2026

LArCADe | Liquid Argon Charge Amplification Devices

The Liquid Argon Charge Amplification Devices (LArCADe) project is an R$\&$D effort aimed at developing instrumentation capable of lowering detection thresholds for ionization signatures in liquid and gaseous argon detectors and achieving O(100 $\mu$m) position resolution. The core concept is the use of sharp “tip arrays” that generate strong local electric-field enhancement, enabling charge amplification and collection with improved spatial resolution. A key physics motivation for this work is to enhance the experimental sensitivity of Coherent Elastic Neutrino-Nucleus Scattering (CEvNS) measurements to low-energy nuclear recoils by enabling spatially resolved charge reconstruction at reduced ionization thresholds, with the goal of achieving event-by-event energy reconstruction for interactions originating from localized accelerator or astrophysical neutrino sources. This poster will present the current status of the instrumentation R$\&$D, which leverages Fermilab’s Noble Liquid Test Facility and UC Santa Barbara’s Nanofabrication Facility, and will discuss the potential physics impact of this technology.

Antonakis, Alexander [UC, Santa Barbara]↗
DOE OSTI2024

System and method for alfvenic reconnecting plasmoid plasma acceleration

According to various embodiments, a system for using magnetic reconnection to accelerate plasma is disclosed. The system includes a pair of electrodes including two concentric rings separated by an electrode gap and held at different electrostatic potential by applying a voltage to generate an inter-electrode electric field. The system further includes a plurality of magnetic coils configured to produce magnetic field lines that connect the pair of electrodes. The system additionally includes a gas injector configured to inject gas into the electrode gap, the injected gas being partially ionized by the inter-electrode electric field to generate a poloidal current that flows along open magnetic field lines across the electrode gap. A total Lorentz force causes oppositely directed magnetic field lines to be expanded around a region of the gas injector to further create an azimuthal current in the form of an axially elongated current sheet that is unstable such that the axially elongated current sheet reconnects and breaks into plasmoids.

Ebrahimi, Fatima Arezu↗
DOE OSTI2017

Influence of Ionization Source Conditions on the Gas-Phase Protomer Distribution of Anilinium and Related Cations

The gas-phase-ion generation technique and specific ion-source settings of a mass spectrometer influence heavily the protonation processes of molecules and the abundance ratio of the generated protomers. Hitherto that has been attributed primarily to the nature of the solvent and the pH. By utilizing electrospray ionization and ion-mobility mass spectrometry (IM-MS), we demonstrate, even in the seemingly trivial case of protonated aniline, that the protomer ratio strongly depends on the source conditions. Under low in-source ion activation, nearly 100% of the N-protomer of aniline is produced, and it can be subsequently converted to the C-protomer by collisional activation effected by increasing the electrical potential difference between the entrance and exit orifices of the first vacuum region. This activation and transformation process takes place even before the ion is mass-selected and subjected to IM separation. Despite the apparent simplicity of the problem, the preferred protonation site of aniline in the gas phase—the amino group or the aromatic ring—has been a topic of controversy. Our results not only provide unambiguous evidence that ring- and nitrogen-protonated aniline can coexist and be interconverted in the gas phase, but also that the ratio of the protomers depends on the internal energy of the original ion. There are many dynamic ion-transformation and fragmentation processes that take place in the different physical compartments of a Synapt G2 HDMS instrument. Such processes can dramatically change the very identity even of small ions, and therefore should be taken into account when interpreting product-ion mass spectra. .

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

Plasma production and composition from hypervelocity impacts on solar cell cover glass

Satellites are subjected to detrimental effects from the space environment, including impacts by orbital debris and meteoroids that can cause mechanical or electrical damage. While mechanical damage is well studied, electrical effects resulting from hypervelocity impact (HVI) remain poorly understood. In HVIs, where the projectile speed exceeds the speed of sound in the target material, the impact energy ionizes the material near the surface, creating a plasma that can cause radio frequency emission. This emission is the main source of electrical anomalies in satellites, but the mechanism behind its creation is still unknown. Ground-based experiments have been used to characterize HVI plasma, including the empirical power law relations that describe the impact charge produced as a function of impactor mass and speed. Quantifying these power law relations gives us a better understanding of the species formed in the impact which can eventually lead to plasma evolution models and help us first, understand the mechanism behind radio frequency emission and second, ways to prevent its damage to the satellites. In this paper, we interpret the results of the HVI experiments on solar cell coverglass targets and identify the potential chemical or molecular reactions that form the impact ion species. This is done by looking simultaneously at multiple data sets for different species within the same impact configuration, and using a new technique for quantifying the power law relations for each emitted species. We use time of flight analysis (TOF) to detect the charged particle compositions and determine their initial speeds. The results suggest that the charge production power law is species specific, with different formation mechanisms involved in a single HVI event, some of which are associated with dissociation and some with ionization of a molecule. Furthermore, our results also show that electrons have different power laws that depend on the spacecraft surface charge. TOF measurements of ions from impact events on solar cell cover glass shows the presence of SiO + and SiO – 2 as the dominant species present in plasmas on positively and negatively charged targets, respectively, as well as the formation of FeO + .

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Detection of Metastatic Breast and Thyroid Cancer in Lymph Nodes by Desorption Electrospray Ionization Mass Spectrometry Imaging

Ambient ionization mass spectrometry has been widely applied to image lipids and metabolites in primary cancer tissues with the purpose of detecting and understanding metabolic changes associated with cancer development and progression. Here, we report the use of desorption electrospray ionization mass spectrometry (DESI-MS) to image metastatic breast and thyroid cancer in human lymph node tissues. Our results show clear alterations in lipid and metabolite distributions detected in the mass spectra profiles from 42 samples of metastatic thyroid tumors, metastatic breast tumors, and normal lymph node tissues. 2D DESI-MS ion images of selected molecular species allowed discrimination and visualization of specific histologic features within tissue sections, including regions of metastatic cancer, adjacent normal lymph node, and fibrosis or adipose tissues, which strongly correlated with pathologic findings. In thyroid cancer metastasis, increased relative abundances of ceramides and glycerophosphoinisitols were observed. In breast cancer metastasis, increased relative abundances of various fatty acids and specific glycerophospholipids were seen. Trends in the alterations in fatty acyl chain composition of lipid species were also observed through detailed mass spectra evaluation and chemical identification of molecular species. The results obtained demonstrate DESI-MSI as a potential clinical tool for the detection of breast and thyroid cancer metastasis in lymph nodes, although further validation is needed. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Oxygen–Chlorine Chemisorption Scaling for Seawater Electrolysis on Transition Metals: The Role of Redox

To clarify what controls species oxidation selectivity in seawater electrolysis, density functional theory (DFT) is used to identify chemisorption enthalpy trends and scaling relations for the simplest relevant adsorbates (O, Cl, and H) on relevant surfaces of 3d transition metals, as well as Pd and Pt, in face-centered-cubic and, if different, their ground-state crystal structures. Approximations are tested for electron exchange-correlation (XC) and van der Waals interactions to assess their ability to reproduce experimental adsorption enthalpies of H and O on Pt(111). The vdW-uncorrected generalized gradient approximation to XC of Perdew, Burke, and Ernzerhof (PBE) agrees most closely with experiments. Using DFT-PBE thereafter, it is determined that the O chemisorption enthalpy on this wide range of transition-metal surfaces is proportional to the sum of first and second atomic ionization energies, akin to a Born–Haber cycle for a redox reaction, indicating that metal redox activity controls O chemisorption strength. Then it is shown that the O and Cl chemisorption enthalpies are strongly correlated, suggesting that the transition metals considered will oxidize unselectively water and Cl – . This strong correlation appears also for crystal reduction potentials of binary oxides and chlorides, indicating a fundamental challenge for future seawater electrode materials design.

08 HYDROGEN↗
DOE OSTI2014

Symmetry-adapted perturbation theory with Kohn-Sham orbitals using non-empirically tuned, long-range-corrected density functionals

The performance of second-order symmetry-adapted perturbation theory (SAPT) calculations using Kohn-Sham (KS) orbitals is evaluated against benchmark results for intermolecular interactions. Unlike previous studies of this “SAPT(KS)” methodology, the present study uses non-empirically tuned long-range corrected (LRC) functionals for the monomers. The proper v{sub xc} (r)→0 asymptotic limit is achieved by tuning the range separation parameter in order to satisfy the condition that the highest occupied KS energy level equals minus the molecule's ionization energy, for each monomer unit. Tests for He{sub 2}, Ne{sub 2}, and the S22 and S66 data sets reveal that this condition is important for accurate prediction of the non-dispersion components of the energy, although errors in SAPT(KS) dispersion energies remain unacceptably large. In conjunction with an empirical dispersion potential, however, the SAPT(KS) method affords good results for S22 and S66, and also accurately predicts the whole potential energy curve for the sandwich isomer of the benzene dimer. Tuned LRC functionals represent an attractive alternative to other asymptotic corrections that have been employed in density-functional-based SAPT calculations, and we recommend the use of tuned LRC functionals in both coupled-perturbed SAPT(DFT) calculations and dispersion-corrected SAPT(KS) calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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