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A machine learning approach for efficient multi-dimensional integration

Many physics problems involve integration in multi-dimensional space whose analytic solution is not available. The integrals can be evaluated using numerical integration methods, but it requires a large computational cost in some cases, so an efficient algorithm plays an important role in solving the physics problems. We propose a novel numerical multi-dimensional integration algorithm using machine learning (ML). After training a ML regression model to mimic a target integrand, the regression model is used to evaluate an approximation of the integral. Then, the difference between the approximation and the true answer is calculated to correct the bias in the approximation of the integral induced by ML prediction errors. Because of the bias correction, the final estimate of the integral is unbiased and has a statistically correct error estimation. Three ML models of multi-layer perceptron, gradient boosting decision tree, and Gaussian process regression algorithms are investigated. The performance of the proposed algorithm is demonstrated on six different families of integrands that typically appear in physics problems at various dimensions and integrand difficulties. The results show that, for the same total number of integrand evaluations, the new algorithm provides integral estimates with more than an order of magnitude smaller uncertainties than those of the VEGAS algorithm in most of the test cases.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

SU-E-T-50: A Multi-Institutional Study of Independent Dose Verification Software Program for Lung SBRT

Purpose: The accuracy of dose distribution depends on treatment planning system especially in heterogeneity-region. The tolerance level (TL) of the secondary check using the independent dose verification may be variable in lung SBRT plans. We conducted a multi-institutional study to evaluate the tolerance level of lung SBRT plans shown in the AAPM TG114. Methods: Five institutes in Japan participated in this study. All of the institutes used a same independent dose verification software program (Simple MU Analysis: SMU, Triangle Product, Ishikawa, JP), which is Clarkson-based and CT images were used to compute radiological path length. Analytical Anisotropic Algorithm (AAA), Pencil Beam Convolution with modified Batho-method (PBC-B) and Adaptive Convolve (AC) were used for lung SBRT planning. A measurement using an ion-chamber was performed in a heterogeneous phantom to compare doses from the three different algorithms and the SMU to the measured dose. In addition to it, a retrospective analysis using clinical lung SBRT plans (547 beams from 77 patients) was conducted to evaluate the confidence limit (CL, Average±2SD) in dose between the three algorithms and the SMU. Results: Compared to the measurement, the AAA showed the larger systematic dose error of 2.9±3.2% than PBC-B and AC. The Clarkson-based SMU showed larger error of 5.8±3.8%. The CLs for clinical plans were 7.7±6.0 % (AAA), 5.3±3.3 % (AC), 5.7±3.4 % (PBC -B), respectively. Conclusion: The TLs from the CLs were evaluated. A Clarkson-based system shows a large systematic variation because of inhomogeneous correction. The AAA showed a significant variation. Thus, we must consider the difference of inhomogeneous correction as well as the dependence of dose calculation engine.

60 APPLIED LIFE SCIENCES↗

2025 Review and Revision of Federal Guidance Report 15

Federal Guidance Report No. 15 (FGR 15), External Exposure to Radionuclides in Air, Water and Soil, published in 2019 and referred to below as FGR 2019, provides age-specific effective dose rate coefficients for reference persons externally exposed to each of 1252 radionuclides homogenously distributed in environmental media. Soon after completion of FGR 2019, the International Commission on Radiological Protection (ICRP) published a similar report (ICRP Publication 144, 2020) addressing the same radionuclides and many of the external exposure scenarios addressed in FGR 2019. In 2023 Argonne National Laboratory (ANL) published a review of dose coefficients in FGR 2019, concluding that “The external effective dose from beta radiation is not appropriately accounted for in FGR 15 for both low- and high-energy beta emitters in air, in soil, and on soil surfaces.” That conclusion was based largely on comparisons of dose coefficients in FGR 2019 with values in ICRP Publication 144 but also on consideration of some unexpected patterns of equivalent dose rate coefficients across tissues and of effective dose rate coefficients across different soil depths, for a selected set of low-energy beta emitters. In response to the ANL report, the Center for Radiation Protection Knowledge (CRPK) at Oak Ridge National Laboratory (ORNL) performed an extensive reexamination of the methods and published values of FGR 2019. CRPK found that coding errors had resulted in inaccurate estimates, primarily overestimates, in many of the dose coefficients tabulated in FGR 2019 but that many of the differences between results in FGR 2019 and ICRP Publication 144 could be traced to differences in methodology. CRPK has corrected all errors in FGR 2019 associated with the coding errors and has taken the opportunity to improve a major portion of the remaining dose coefficients in FGR 2019, primarily through additional Monte Carlo calculations resulting in improved statistics for tissue equivalent dose rate coefficients for exposure to monoenergetic sources. This has eliminated the need for extrapolation of results from high and medium energies to low energies, as was done in FGR 2019. In addition, inconsistencies in the methodology identified in the review, such as computational representation of the adult female, were eliminated. The revised effective dose rate coefficients are consistent with values in ICRP Publication 144 except for differences in values clearly arising from differences in methodology; and differences in values for a relatively small set of very low-energy radionuclides with highly uncertain dose coefficients regardless of methodology.

54 ENVIRONMENTAL SCIENCES↗

Clinical Evaluation of a Robotic 6-Degree of Freedom Treatment Couch for Frameless Radiosurgery

Purpose: To evaluate the added value of 6-degree of freedom (DOF) patient positioning with a robotic couch compared with 4DOF positioning for intracranial lesions and to estimate the immobilization characteristics of the BrainLAB frameless mask (BrainLAB AG, Feldkirchen, Germany), more specifically, the setup errors and intrafraction motion. Methods and Materials: We enrolled 40 patients with 66 brain metastases treated with frameless stereotactic radiosurgery and a 6DOF robotic couch. Patient positioning was performed with the BrainLAB ExacTrac stereoscopic X-ray system. Positioning results were collected before and after treatment to assess patient setup error and intrafraction motion. Existing treatment planning data were loaded and simulated for 4DOF positioning and compared with the 6DOF positioning. The clinical relevance was analyzed by means of the Paddick conformity index and the ratio of prescribed isodose volume covered with 4DOF to that obtained with the 6DOF positioning. Results: The mean three-dimensional setup error before 6DOF correction was 1.91 mm (SD, 1.25 mm). The rotational errors were larger in the longitudinal (mean, 0.23 Degree-Sign ; SD, 0.82 Degree-Sign ) direction compared with the lateral (mean, -0.09 Degree-Sign ; SD, 0.72 Degree-Sign ) and vertical (mean, -0.10 Degree-Sign ; SD, 1.03 Degree-Sign ) directions (p < 0.05). The mean three-dimensional intrafraction shift was 0.58 mm (SD, 0.42 mm). The mean intrafractional rotational errors were comparable for the vertical, longitudinal, and lateral directions: 0.01 Degree-Sign (SD, 0.35 Degree-Sign ), 0.03 Degree-Sign (SD, 0.31 Degree-Sign ), and -0.03 Degree-Sign (SD, 0.33 Degree-Sign ), respectively. The mean conformity index decreased from 0.68 (SD, 0.08) (6DOF) to 0.59 (SD, 0.12) (4DOF) (p < 0.05). A loss of prescribed isodose coverage of 5% (SD, 0.08) was found with the 4DOF positioning (p < 0.05). Half a degree for longitudinal and lateral rotations can be identified as a threshold for coverage loss. Conclusions: With a mask immobilization, patient setup error and intrafraction motions need to be evaluated and corrected for. The 6DOF patient positioning with a 6DOF robotic couch to correct translational and rotational setup errors improves target positioning with respect to treatment isocenter, which is in direct relation with the clinical outcome, compared with the 4DOF positioning.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Measurement of cardiac output from dynamic pulmonary circulation time CT

Purpose: To introduce a method of estimating cardiac output from the dynamic pulmonary circulation time CT that is primarily used to determine the optimal time window of CT pulmonary angiography (CTPA). Methods: Dynamic pulmonary circulation time CT series, acquired for eight patients, were retrospectively analyzed. The dynamic CT series was acquired, prior to the main CTPA, in cine mode (1 frame/s) for a single slice at the level of the main pulmonary artery covering the cross sections of ascending aorta (AA) and descending aorta (DA) during the infusion of iodinated contrast. The time series of contrast changes obtained for DA, which is the downstream of AA, was assumed to be related to the time series for AA by the convolution with a delay function. The delay time constant in the delay function, representing the average time interval between the cross sections of AA and DA, was determined by least square error fitting between the convoluted AA time series and the DA time series. The cardiac output was then calculated by dividing the volume of the aortic arch between the cross sections of AA and DA (estimated from the single slice CT image) by the average time interval, and multiplying the result by a correction factor. Results: The mean cardiac output value for the six patients was 5.11 (l/min) (with a standard deviation of 1.57 l/min), which is in good agreement with the literature value; the data for the other two patients were too noisy for processing. Conclusions: The dynamic single-slice pulmonary circulation time CT series also can be used to estimate cardiac output.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Using Density-Corrected DFT to Understand Density-Driven and Functional-Dependent Errors in Ab Initio Simulations of the Hydrated Electron

The hydrated electron, an excess electron in liquid water, plays a crucial role in a plethora of chemical processes, motivating extensive research efforts to characterize its structure, dynamics, and reactivity in solution. Recent theoretical approaches to understanding this intriguing object have involved ab initio simulations based on density functional theory (DFT). Although DFT allows for the study of hydrated electron reactivity and quantum mechanical behavior, it is well-known that anionic systems can suffer from significant density-driven errors (DDEs). Density-corrected DFT (DC-DFT) provides a framework to mitigate such errors; the method reduces DDEs by replacing the self-consistent (SC) density associated with a given density functional with the Hartree–Fock (HF) density. Since HF densities tend to be more localized than DFT SC densities, the DC-DFT scheme significantly improves errors in calculations where the SC density is spuriously delocalized. Here, we investigate how the use of density correction affects the calculated properties of the DFT-simulated (PBEh) hydrated electron, a particularly challenging diffuse anionic system to simulate. First, we analyze charge delocalization in a system consisting of a model octahedral hydrated electron water cluster (the so-called Kevan structure) along with a spatially separated sulfur atom. We show that the use of density correction indeed reduces DDEs in comparison to a standard DFT global hybrid functional. We then propagate molecular dynamics trajectories of the hydrated electron using DC-DFT, where we find that DC further localizes electron density in the cavity region, a signature of reduced charge delocalization. Unfortunately, the decreased radius of gyration of the spin density and corresponding tightening of the local solvation structure from density correction causes predicted observables to deviate further from experimental measurements than when density correction is not employed. Here, we argue that DC’s worse agreement with experiment results from the removal of a fortuitous cancellation of errors that is intrinsic to the PBEh functional. This indicates that the difficulties with DFT to simulate hydrated electrons are primarily due to the inherent approximations in DFT rather than to density-driven errors.

Density functional theory↗

Adaptive optical correction for in vivo two-photon fluorescence microscopy with neural fields

Adaptive optics restore ideal imaging performance in complex samples by measuring and correcting optical aberrations but often require custom-built microscopes with carefully aligned wavefront sensing/shaping devices and can be susceptible to sample motion. Here we describe NeAT, a computational framework using neural fields for adaptive optics two-photon fluorescence microscopy. NeAT estimates wavefront aberration and recovers sample structure from a 3D image stack without requiring external datasets for training. Incorporating motion correction in learning and correcting conjugation errors commonly found in commercial microscopes, NeAT is designed for deployment in biological laboratories for in vivo imaging. We validate NeAT’s performance using a custom-built microscope with a wavefront sensor under varying signal-to-noise ratios, aberration and motion conditions. With a commercial microscope, we demonstrate real-time aberration correction for in vivo morphological and functional imaging in the living mouse brain, with NeAT improving the signal and accuracy of glutamate and calcium imaging of synapses and neurons.

Kang, Iksung↗

Reply to ''Comment on 'Modal expansion approach to optical-frequency-comb generation with monolithic whispering-gallery-mode resonators'''

In a Comment [Deych, Phys. Rev. A 84, 017801 (2011)] on our recent article [Chembo and Yu, Phys. Rev. A 82, 033801 (2010)] on Kerr comb generation in monolithic whispering-gallery-mode (WGM) resonators, the author claims that even though our main results ''remain intact'', the framework of our analysis contains some mathematical errors. In this Reply, we demonstrate that the author's criticisms and his alternative theory are incorrect, and that all the disagreeing claims come from the author's misunderstanding of the physical system under investigation. In particular, the main conceptual error in the Comment is the confusion between evanescent and radiative coupling mechanisms for WGM resonators (in terms of Q factor, this is in our case a confusion between {approx}10{sup 9} and {approx}10{sup 2000}, respectively). This essential misconception leads for example the author to introduce a nonphysical {approx}10{sup 2000} multiplicative correction factor for the laser pump power. We show in this Reply that our WGM resonators are radiatively closed (because of the quasi-infinite radiative Q factor), so that the Mie scattering formalism proposed by Deych, which relies on radiative coupling, can only lead to erroneous results. We also show that the modal expansion approach in our original paper is appropriate, and all our approximations are physically well justified. We therefore stand by our modeling results, which are moreover in excellent agreement with the experiments reported in [Chembo, Strekalov, and Yu, Phys. Rev. Lett. 104, 103902 (2010)].

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Virtex-5QV Self Scrubber

This HDL code (hereafter referred to as "software") implements circuitry in Xilinx Virtex-5QV Field Programmable Gate Array (FPGA) hardware. This software allows the device to self-check the consistency of its own configuration memory for radiation-induced errors. The software then provides the capability to correct any single-bit errors detected in the memory using the device's inherent circuitry, or reload corrupted memory frames when larger errors occur that cannot be corrected with the device's built-in error correction and detection scheme.

Wojahn, Christopher K.↗

An Evolve-Then-Correct Reduced Order Model for Hidden Fluid Dynamics

In this paper, we put forth an evolve-then-correct reduced order modeling approach that combines intrusive and nonintrusive models to take hidden physical processes into account. Specifically, we split the underlying dynamics into known and unknown components. In the known part, we first utilize an intrusive Galerkin method projected on a set of basis functions obtained by proper orthogonal decomposition. We then present two variants of correction formula based on the assumption that the observed data are a manifestation of all relevant processes. The first method uses a standard least-squares regression with a quadratic approximation and requires solving a rank-deficient linear system, while the second approach employs a recurrent neural network emulator to account for the correction term. We further enhance our approach by using an orthonormality conforming basis interpolation approach on a Grassmannian manifold to address off-design conditions. The proposed framework is illustrated here with the application of two-dimensional co-rotating vortex simulations under modeling uncertainty. The results demonstrate highly accurate predictions underlining the effectiveness of the evolve-then-correct approach toward real-time simulations, where the full process model is not known a priori.

long short-term memory↗

SU-E-T-790: Validation of 4D Measurement-Guided Dose Reconstruction (MGDR) with OCTAVIUS 4D System

Purpose: To validate the MGDR of OCTAVIUS 4D system (PTW, Freiburg, Germany) for quality assurance (QA) of volumetric-modulated arc radiotherapy (VMAT). Methods: 4D-MGDR measurements were divided into two parts: 1) square fields from 2×2 to 25×25 cm{sup 2} at 0°, 10° and 45° gantry, and 2) 8 VMAT plans (5 nasopharyngeal and 3 prostate) collapsed to gantry 40° in QA mode in Monaco v5.0 (Elekta, CMS, Maryland Heights, MO) were delivered on the OCTAVIUS 4D phantom with the OCTAVIUS 1500 detector plane perpendicular to either the incident beam to obtain the reconstructed dose (OCTA4D) or the 0° gantry axis to obtain the raw doses (OCTA3D) in Verisoft 6.1 (PTW, Freiburg, Germany). Raw measurements of OCTA3D were limited to < 45° gantry to avoid >0.5% variation of detector angular response with respect to 0° gantry as determined previously. Reconstructed OCTA4D and raw OCTA3D doses for all plans were compared at the same detector plane using γ criteria of 2% (local dose)/2mm and 3%/3mm criteria. Results: At gantry 0° and 10°, the γ results for all OCTA4D on detector plane coinciding with OCTA3D were over 90% at 2%/2mm except for the largest field (25×25 cm{sup 2} ) showing >88%. For square field at 45° gantry, γ passing rate is > 90% for fields smaller than 15x 15cm2 but < 80% for field size of 20 x20 cm{sup 2} upward. For VMAT, γ results showed 94% and 99% passing rate at 2%/2mm and 3%/3mm, respectively. Conclusion: OCTAVIUS 4D system has compromised accuracy in reconstructing dose away from the central beam axis, possibly due to the off-axis softening correction and errors of the percent depth dose data necessary as input for MGDR. Good results in VMAT delivery suggested that the system is relatively reliable for VMAT with small segments.

60 APPLIED LIFE SCIENCES↗

A constraint on the formation timescale of the young open cluster NGC 2264: lithium abundance of pre-main sequence stars

The timescale of cluster formation is an essential parameter in order to understand the formation process of star clusters. Pre-main sequence (PMS) stars in nearby young open clusters reveal a large spread in brightness. If the spread were considered to be a result of a real spread in age, the corresponding cluster formation timescale would be about 5–20 Myr. Hence it could be interpreted that star formation in an open cluster is prolonged for up to a few tens of Myr. However, difficulties in reddening correction, observational errors, and systematic uncertainties introduced by imperfect evolutionary models for PMS stars can result in an artificial age spread. Alternatively, we can utilize Li abundance as a relative age indicator of PMS star to determine the cluster formation timescale. The optical spectra of 134 PMS stars in NGC 2264 have been obtained with MMT/Hectochelle. The equivalent widths have been measured for 86 PMS stars with a detectable Li line (3500<T{sub eff}[K]⩽6500). Li abundance under the condition of local thermodynamic equilibrium (LTE) was derived using the conventional curve of growth method. After correction for non-LTE effects, we find that the initial Li abundance of NGC 2264 is A(Li)=3.2±0.2. From the distribution of the Li abundances, the underlying age spread of the visible PMS stars is estimated to be about 3–4 Myr and this, together with the presence of embedded populations in NGC 2264, suggests that the cluster formed on a timescale shorter than 5 Myr.

79 ASTRONOMY AND ASTROPHYSICS↗

The many-body expansion for aqueous systems revisited: II. Alkali metal and halide ion – water interactions

We present a detailed study of the Many-Body Expansion (MBE) for alkali metal and halide ion-water interactions and quantify the effect of these ions on the strength of the surrounding aqueous hydrogen bonding environment. Building on our previous work on neutral water clusters [J. P. Heindel and S. S. Xantheas, J. Chem. Theor. Comput. 16 (11), 6843–6855 (2020)], we carry out the complete MBE for ion-water clusters, Z+/-(H2O)9, where Z = Li+, K+, Cs+, Cl-, Br-, I- and compare with the results for (H2O)10. The 2-B ion-water (I-W) interaction represents a larger percentage of the total cluster binding energy compared to a pure water cluster of the same size with the total 3-B term being smaller and of opposite sign (repulsive) whereas higher order terms are essentially negligible. The same oscillating behavior around zero for MBE terms higher than the 5-B with basis set that was reported for water clusters is also observed for the ion-water clusters considered with Basis Set Superposition Error (BSSE) corrections amending this like in the water cluster case. A remarkable, linear anti-correlation between the total 2-B ion-water and the total 2-B and 3-B water-water interactions is found, quantifying the effect of the different ions in disrupting and altering (weakening) the neighboring hydrogen bonded water network. Our results suggest a universal behavior of the two different families of ions (alkali metals and halides) for both the correlations of the various components of the total binding energies as well as the estimate of the 2-B BSSE correction which is reported to follow a common profile for ion-water and water-water interactions when cast in terms of reduced distances and energies. We expect our insights into the nature of BSSE will be important for future ab initio based, many-body molecular dynamics studies.

ion-water interactions, water-water interaction, m↗

Fixing the reference frame for PPMXL proper motions using extragalactic sources

In this study, we quantify and correct systematic errors in PPMXL proper motions using extragalactic sources from the first two LAMOST data releases and the Vèron-Cetty & Vèron Catalog of Quasars. Although the majority of the sources are from the Vèron catalog, LAMOST makes important contributions in regions that are not well-sampled by previous catalogs, particularly at low Galactic latitudes and in the south Galactic cap. We show that quasars in PPMXL have measurable and significant proper motions, which reflect the systematic zero-point offsets present in the catalog. We confirm the global proper motion shifts seen by Wu et al., and additionally find smaller-scale fluctuations of the QSO-derived corrections to an absolute frame. Finally, we average the proper motions of 158 106 extragalactic objects in bins of 3° × 3° and present a table of proper motion corrections.

79 ASTRONOMY AND ASTROPHYSICS↗

Erratum: A Comparison of Closures for Stochastic Advection-Diffusion Equations

This note corrects an error in the authors' article [SIAM/ASA J. Uncertain. Quantif., 1 (2013), pp. 319 347] in which the cited work [Neuman, Water Resour. Res., 29(3) (1993), pp. 633 645] was incorrectly represented and attributed. Concentration covariance equations presented in our article as new were in fact previously derived in the latter work. In the original abstract, the phrase " . . .we propose a closed-form approximation to two-point covariance as a measure of uncertainty. . ." should be replaced by the phrase " . . .we study a closed-form approximation to two-point covariance, previously derived in [Neuman 1993], as a measure of uncertainty." The primary results in our article--the analytical and numerical comparison of existing closure methods for specific example problems are not changed by this correction.

stochastic PDE↗

Comparing the performance of density functionals in describing the adsorption of atoms and small molecules on Ni(111)

Reaction networks calculated using density functional theory (DFT) play a crucial role in understanding and predicting heterogeneous catalyst performance. However, results obtained using different density functionals can vary significantly. Accordingly, it is important to assess the accuracy of available functionals in capturing adsorption energetics derived from single-crystal adsorption microcalorimetry experiments. Here, we evaluate how different density functionals describe the molecular and dissociative adsorption of CH 3 I, the adsorption of CH 3 , I, and H, and the dissociative adsorption of CH 4 on Ni(111). First, we identify energetically-preferred adsorbed states for each adsorbate at three surface coverages and calculate the corresponding enthalpies of adsorption at 160 K. Then, we compare the results to experimental measurements published in the literature. For each adsorption process we find at least one functional that is quantitatively accurate within experimental error, but no functional is accurate (within experimental error) for all adsorption processes studied. Even when assuming an additional DFT error of ±20 kJ/mol on top of the experimental error, only the PBE-D3 and RPBE-D3 functionals are accurate for all considered adsorption systems. Overall, these results indicate that quantitative agreement between density functional theory calculations and experimental measurements is both system- and functional-dependent. Importantly, single-crystal adsorption microcalorimetry experiments will continue to play an important role for benchmarking density functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The dosimetric impact of daily setup error on target volumes and surrounding normal tissue in the treatment of prostate cancer with intensity-modulated radiation therapy

The purpose of this study was to evaluate the impact of daily setup error and interfraction organ motion on the overall dosimetric radiation treatment plans. Twelve patients undergoing definitive intensity-modulated radiation therapy (IMRT) treatments for prostate cancer were evaluated in this institutional review board-approved study. Each patient had fiducial markers placed into the prostate gland before treatment planning computed tomography scan. IMRT plans were generated using the Eclipse treatment planning system. Each patient was treated to a dose of 8100 cGy given in 45 fractions. In this study, we retrospectively created a plan for each treatment day that had a shift available. To calculate the dose, the patient would have received under this plan, we mathematically 'negated' the shift by moving the isocenter in the exact opposite direction of the shift. The individualized daily plans were combined to generate an overall plan sum. The dose distributions from these plans were compared with the treatment plans that were used to treat the patients. Three-hundred ninety daily shifts were negated and their corresponding plans evaluated. The mean isocenter shift based on the location of the fiducial markers was 3.3 {+-} 6.5 mm to the right, 1.6 {+-} 5.1 mm posteriorly, and 1.0 {+-} 5.0 mm along the caudal direction. The mean D95 doses for the prostate gland when setup error was corrected and uncorrected were 8228 and 7844 cGy (p < 0.002), respectively, and for the planning target volume (PTV8100) was 8089 and 7303 cGy (p < 0.001), respectively. The mean V95 values when patient setup was corrected and uncorrected were 99.9% and 87.3%, respectively, for the PTV8100 volume (p < 0.0001). At an individual patient level, the difference in the D95 value for the prostate volume could be >1200 cGy and for the PTV8100 could approach almost 2000 cGy when comparing corrected against uncorrected plans. There was no statistically significant difference in the D35 parameter for the surrounding normal tissue except for the dose received by the penile bulb and the right hip. Our dosimetric evaluation suggests significant underdosing with inaccurate target localization and emphasizes the importance of accurate patient setup and target localization. Further studies are needed to evaluate the impact of intrafraction organ motion, rotation, and deformation on doses delivered to target volumes.

61 RADIATION PROTECTION AND DOSIMETRY↗

Revisiting Competing Paths in Electrochemical CO 2 Reduction on Copper via Embedded Correlated Wavefunction Theory

We re-evaluate two key steps in the mechanism of CO 2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO 2 reduction, which is the subject of ongoing work.

30 DIRECT ENERGY CONVERSION↗