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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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At least 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Microstructure and residual elastic strain at graphite nodules in ductile cast iron analyzed by synchrotron X-ray microdiffraction

The microstructure and residual elastic strain at graphite nodules (GNs) in ductile cast iron produced using either a fast or slow cooling rate have been characterized using synchrotron 3D X-ray Laue microdiffraction. The results demonstrate that thermal stress is introduced during cooling and that part of this stress is relaxed by plastic deformation of the polycrystalline ferrite matrix. It is observed that the plastic deformation is accommodated by the formation of dislocations and dislocation boundaries, which are organized in a cell structure. The dislocation density quantified based on the microstructure is most pronounced at the GN/matrix interface around small GNs in the fast cooled sample. Residual elastic strain is also present, which is mainly compressive with a maximum of 6.0–9.9 × 10 -4 near the GNs. Gradients of plastic deformation and elastic strain field around the GNs are observed. The results document for the first time that both the elastic strain field and the plastic strain field averaged over the grains around the GNs is approximately scaling with GN size and not affected by the cooling rate. The experimental data are compared with simulations by a finite element method, and agreement and disagreement are considered in detail.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Variational Discrete Action Theory

In this work, we propose the variational discrete action theory (VDAT) to study the ground state properties of quantum many-body Hamiltonians. VDAT is a variational theory based on the sequential product density matrix (SPD) ansatz, characterized by an integer $\mathscr{N}$, which monotonically approaches the exact solution with increasing $\mathscr{N}$. To evaluate the SPD, we introduce a discrete action and a corresponding integer time Green’s function. We use VDAT to exactly evaluate the SPD in two canonical models of interacting electrons: the Anderson impurity model and the d = ∞ Hubbard model. For the latter, we evaluate $\mathscr{N}$ = 2 – 4, where $\mathscr{N}$ = 2 recovers the Gutzwiller approximation (GA), and we show that $\mathscr{N}$ = 3, which exactly evaluates the Gutzwiller-Baeriswyl wave function, provides a truly minimal yet precise description of Mott physics with a cost similar to that of the GA. VDAT is a flexible theory for studying quantum Hamiltonians, competing both with state-of-the-art methods and simple, efficient approaches all within a single framework.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

SU-D-213-04: Accounting for Volume Averaging and Material Composition Effects in An Ionization Chamber Array for Patient Specific QA

Purpose: This study explores novel methods to address two significant challenges affecting measurement of patient-specific quality assurance (QA) with IBA’s Matrixx Evolution™ ionization chamber array. First, dose calculation algorithms often struggle to accurately determine dose to the chamber array due to CT artifact and algorithm limitations. Second, finite chamber size and volume averaging effects cause additional deviation from the calculated dose. Methods: QA measurements were taken with the Matrixx positioned on the treatment table in a solid-water Multi-Cube™ phantom. To reduce the effect of CT artifact, the Matrixx CT image set was masked with appropriate materials and densities. Individual ionization chambers were masked as air, while the high-z electronic backplane and remaining solid-water material were masked as aluminum and water, respectively. Dose calculation was done using Varian’s Acuros XB™ (V11) algorithm, which is capable of predicting dose more accurately in non-biologic materials due to its consideration of each material’s atomic properties. Finally, the exported TPS dose was processed using an in-house algorithm (MATLAB) to assign the volume averaged TPS dose to each element of a corresponding 2-D matrix. This matrix was used for comparison with the measured dose. Square fields at regularly-spaced gantry angles, as well as selected patient plans were analyzed. Results: Analyzed plans showed improved agreement, with the average gamma passing rate increasing from 94 to 98%. Correction factors necessary for chamber angular dependence were reduced by 67% compared to factors measured previously, indicating that previously measured factors corrected for dose calculation errors in addition to true chamber angular dependence. Conclusion: By comparing volume averaged dose, calculated with a capable dose engine, on a phantom masked with correct materials and densities, QA results obtained with the Matrixx Evolution™ can be significantly improved. In addition, necessary correction factors are reduced, allowing for more reliable and meaningful patient-specific QA measurements.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Phase-field modeling of radiation-induced segregation for multicomponent alloys

Structural alloys under irradiation are known to undergo radiation-induced solute redistribution (RIS) at grain boundaries, leading to detrimental effects such as intergranular corrosion and stress-assisted cracking. To better understand the phenomenon, improved models of RIS applicable to concentrated, multicomponent alloys, and mesoscale microstructures are needed. In this talk, we present a novel grand-potential-based phase-field model to account for the complete set of multicomponent kinetic and thermodynamic couplings between atoms and point defects in the Onsager transport equations. We demonstrate multiscale modeling capability by deriving the Onsager coefficient matrix from atomistic-based Kinetic Monte Carlo simulations. Model predictions and validations of RIS and the effect of defect production, grain boundary sink strength and density are demonstrated for a model FCC FeCrNi system. We also demonstrate the novel capability to describe RIS in the presence of equilibrium segregation described using a density-based CALPHAD thermodynamic framework. This modeling approach overcomes certain limitations in conventional RIS models and provides a step closer towards multiscale modeling.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Electron–phonon physics from first principles using the EPW code

EPW is an open-source software for ab initio calculations of electron–phonon interactions and related materials properties. The code combines density functional perturbation theory and maximally localized Wannier functions to efficiently compute electron–phonon coupling matrix elements, and to perform predictive calculations of temperature-dependent properties and phonon-assisted quantum processes in bulk solids and low-dimensional materials. Here, we report on significant developments in the code since 2016, namely: a transport module for the calculation of charge carrier mobility under electric and magnetic fields using the Boltzmann transport equation; a superconductivity module for calculations of phonon-mediated superconductors using the anisotropic multi-band Eliashberg theory; an optics module for calculations of phonon-assisted indirect transitions; a module for the calculation of small and large polarons without supercells; and a module for calculating band structure renormalization and temperature-dependent optical spectra using the special displacement method. For each capability, we outline the methodology and implementation and provide example calculations.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Self-assembled Co-BaZrO 3 nanocomposite thin films with ultra-fine vertically aligned Co nanopillars

A simple one-step pulsed laser deposition (PLD) method has been applied to grow self-assembled metal-oxide nanocomposite thin films. The as-deposited Co-BaZrO 3 films show high epitaxial quality with ultra-fine vertically aligned Co nanopillars (diameter <5 nm) embeded in BZO matrix. The diameter of the nanopillars can be further tuned by varying the deposition frequency. The metal and oxide phases grow separately without inter-diffusion or mixing. Taking advantage of this unique structure, a high saturation magnetization of ~1375 emu/cm 3 in the Co- BaZrO 3 nanocomposites has been achieved and further confirmed by Lorentz microscopy imaging in TEM. Furthermore, the coercivity values of this nanocomposite thin films range from 600 Oe (20 Hz) to 1020 Oe (2 Hz), which makes the nanocomposite an ideal candidate for high-density perpendicular recording media.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Accelerating molecular property calculations with nonorthonormal Krylov space methods

Here, we formulate Krylov space methods for large eigenvalue problems and linear equation systems that take advantage of decreasing residual norms to reduce the cost of matrix-vector multiplication. The residuals are used as subspace basis without prior orthonormalization, which leads to generalized eigenvalue problems or linear equation systems on the Krylov space. These nonorthonormal Krylov space (nKs) algorithms are favorable for large matrices with irregular sparsity patterns whose elements are computed on the fly, because fewer operations are necessary as the residual norm decreases as compared to the conventional method, while errors in the desired eigenpairs and solution vectors remain small. We consider real symmetric and symplectic eigenvalue problems as well as linear equation systems and Sylvester equations as they appear in configuration interaction and response theory. The nKs method can be implemented in existing electronic structure codes with minor modifications and yields speed-ups of 1.2-1.8 in typical time-dependent Hartree-Fock and density functional applications without accuracy loss. The algorithm can compute entire linear subspaces simultaneously which benefits electronic spectra and force constant calculations requiring many eigenpairs or solution vectors. The nKs approach is related to difference density methods in electronic ground state calculations, and particularly efficient for integral direct computations of exchange-type contractions. By combination with resolution-of-the-identity methods for Coulomb contractions, three- to fivefold speed-ups of hybrid time-dependent density functional excited state and response calculations are achieved.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2012

Novel, dually radiolabeled peptides for simultaneous monitoring of enzymatic activity and protein targets

This application investigated a novel imaging approach to develop methods to incorporate multiple radionuclides into a single peptide at chemoselective sites for simultaneous monitoring of cell-bound protein targets as well as specific enzymatic activity, both of which are associated with enhanced tumor growth and metastasis. This imaging construct was synthesized in such a manner so that the PET radionuclide will remain associated with the tumor cells and the SPECT radionuclide was cleaved from the imaging agent. Measurement of the PET agent only will yield information about the tumor marker density while measurement of the amount of co-localization and mismatch of the two radionuclides will yield information about the enzymatic activity. This coincident measuring technique using both PET and SPECT agents allows us to draw correlations involving the interactions of enzymes (cathepsin, serine-protease urokinase (uPA) and matrix metalloproteases) and other cellular proteins which play a role in cancer growth and metastasis. This technique will allow for studies in xenograft or genetic models of cancer in the same animal at the same time, thus eliminating problems that may occur when trying to invoke comparisons across animals or timepoints. By using radionuclide imaging as opposed to other imaging modalities, this technique has the potential to be translatable and can exploit the high specific activity probes which can be generated with radiotracers. The proof of principle test of this system investigated simultaneous monitoring of matrix metalloprotease (MMP) activity in the extracellular matrix (ECM) as well as density of integrins on the cell surface, both of which can serve as tumor markers. The outcomes/deliverables of this project were as follows: 1. Peptides were synthesized dually labeled at chemospecific sites with PET and SPECT agents. 2. Stability (intrinsic and to radiolysis) and specific activity of these labeled compounds were determined. 3. The feasibility of using these agents for simultaneous monitoring of MMP-2 enzymatic activity and $\alpha v \beta 3$ integrin density was demonstrated in several in vitro assays Radiotracers can be detected at concentrations up to 1000 fold lower than those labeled with non-radioactive markers (e.g. MRI contrast agents), thus using this technique has the advantage of very high sensitivity to measure these processes in vivo. Hence, the development of an efficient approach to the dual labeling of these molecular probes is embodied within this project, with the end result yielding a molecular imaging probe with the highest specific activity possible. An advantage to this dual labeling approach is the ability to measure two different biochemical processes at the same time, a benefit which is not possible in scans involving protocols utilizing two different radiolabeled agents injected sequentially. Another advantage to this technique is the ability to measure enzymatic activity in the form of substrate cleavage. This can only be achieved with a dually labeled compound as has been demonstrated in the case of FRET1. To our knowledge this is the first instance of a measurement of enzymatic substrate cleavage by a dually labeled PET/SPECT radionuclide imaging agent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2018

A practical computational method for the anisotropic redshift-space three-point correlation function

Here, we present an algorithm enabling computation of the anisotropic redshift-space galaxy threepoint correlation function ( 3 PCF) scaling as N 2 , with N the number of galaxies. Our previous work showed how to compute the isotropic 3 PCF with this scaling by expanding the radially binned density field around each galaxy in the survey into spherical harmonics and combining these coefficients to form multipole moments. The N 2 scaling occurred because this approach never explicitly required the relative angle between a galaxy pair about the primary galaxy. Here, we generalize this work, demonstrating that in the presence of azimuthally symmetric anisotropy produced by redshift-space distortions (RSD), the 3 PCF can be described by two triangle side lengths, two independent total angular momenta, and a spin. This basis for the anisotropic 3 PCF allows its computation with negligible additional work over the isotropic 3 PCF. We also present the covariance matrix of the anisotropic 3 PCF measured in this basis. Our algorithm tracks the full 5 D redshift-space 3 PCF, uses an accurate line of sight to each triplet, is exact in angle, and easily handles edge correction. It will enable use of the anisotropic large-scale 3 PCF as a probe of RSD in current and upcoming large-scale redshift surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Structural Analysis of ZnO Nanoparticles Reinforced P(3HB-co-15 mol% 3HHx) Bioplastic Composite

Bioplastics are gaining interest due to their biodegradable and biocompatible nature which can be used as a replacement for petroleum based plastics. Poly (3-hydroxybutyrate-co-15 mol% 3-hydroxyhexanoate) [P(3HB-co-15 mol% 3HHx)]/ZnO nanoparticles (NPs) blended bioplastic films were fabricated by solution casting method using chloroform as solvent. The structural characteristics such as peak intensity analysis, crystallite size, dislocation density, and texture coefficient of ZnO NPs mixed P(3HB-co-15 mol% 3HHx) samples were studied using X-Ray Diffraction (XRD) and Fourier Transform Infra-Red (FTIR) analyses. It is clear from the XRD analyses that the crystallinity of P(3HB-co-15 mol% 3HHx) was decreased considerably as ZnO NPs concentration increased. The crystallite size of P(3HB-co-15 mol% 3HHx) was decreased with an increase in ZnO NPs concentration and observed within 150 nm and the dislocation density was decreased with respect to the orientation of P(3HB-co-15 mol% 3HHx) crystals. Simultaneously, the structural properties of ZnO NPs in P(3HB-co-15 mol% 3HHx) matrix were affected noticeably with respect to the ZnO NPs and copolymer concentrations. The characteristic peak positions from FTIR spectra of P(3HB-co-15 mol% 3HHx) copolymer shifted towards higher frequency and evidenced the existence of structural defects. Overall, it was found from both XRD and FTIR analyses that the presence of ZnO NPs affected the crystallinity of P(3HB-co-15 mol% 3HHx) copolymer due to the formation of intermolecular bonds, which restricted the preferential orientation of P(3HB-co-15 mol% 3HHx) molecules which was observed from the texture coefficient analyses. Based on these observations, ZnO NPs at low concentrations can be used with P(3HB-co-15 mol% 3HHx) copolymer effectively and the resulting composite may be used for packaging application.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

High-performance polyimide nanocomposites with core-shell AgNWs@BN for electronic packagings

The increasing density of electronic devices underscores the need for efficient thermal management. Silver nanowires (AgNWs), as one-dimensional nanostructures, possess a high aspect ratio and intrinsic thermal conductivity. However, high electrical conductivity of AgNWs limits their application for electronic packaging. We synthesized boron nitride-coated silver nanowires (AgNWs@BN) using a flexible and fast method followed by incorporation into synthetic polyimide (PI) for enhanced thermal conductivity and dielectric properties of nanocomposites. The thinner boron nitride intermediate nanolayer on AgNWs not only alleviated the mismatch between AgNWs and PI but also enhanced their interfacial interaction. Hence, the maximum thermal conductivity of an AgNWs@BN/PI composite with a filler loading up to 20% volume was increased to 4.33 W/m K, which is an enhancement by nearly 23.3 times compared with that of the PI matrix. The relative permittivity and dielectric loss were about 9.89 and 0.015 at 1 MHz, respectively. Compared with AgNWs@SiO{sub 2}/PI and Ag@BN/PI composites, boron nitride-coated core-shell structures effectively increased the thermal conductivity and reduced the permittivity of nanocomposites. The relative mechanism was studied and discussed. This study enables the identification of appropriate modifier fillers for polymer matrix nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Analytic error analysis of cross section interpolation methods in nodal diffusion codes - II: Numerical results

This paper is the second part of a two-part paper that documents the numerical results for the partial derivatives model presented in part I. In this paper, we derive the error bounds for the analytical point-wise error expression and verify our bounds with numerical experiments. The point-wise error expressions make available, and bound, the sources that contribute to the total error of the interpolated cross section in terms of the Lagrange interpolation errors and the model form error. MPACT is used to generate two-group homogenized cross sections for Westinghouse's AP1000 Region 4 lattice to evaluate the accuracy of the bounds. Error bounds calculated over a grid are compared to numerical data for uni-variate and multi-variate interpolation. The point-wise error bounds of a typical case matrix - two branches in each state variable - are displayed for bi-variate interpolation in the state variables: moderator density, fuel temperature, and boron concentration. The error bounds are shown to be highly accurate compared to numerical results, and in accordance with the underlying physics. We then discuss and show how the sources of error contribute to the total error, and consider the improvement of each error source. Finally, we mention future work such as propagating our cross section error bounds through a reactivity calculation. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2018

Correlation matrix renormalization theory for correlated-electron materials with application to the crystalline phases of atomic hydrogen

Developing accurate and computationally efficient methods to calculate the electronic structure and total energy of correlated-electron materials has been a very challenging task in condensed matter physics and materials science. Recently, we have developed a correlation matrix renormalization (CMR) method which does not assume any empirical Coulomb interaction U parameters and does not have double counting problems in the ground-state total energy calculation. The CMR method has been demonstrated to be accurate in describing both the bonding and bond breaking behaviors of molecules. In this study, we extend the CMR method to the treatment of electron correlations in periodic solid systems. By using a linear hydrogen chain as a benchmark system, we show that the results from the CMR method compare very well with those obtained recently by accurate quantum Monte Carlo (QMC) calculations. We also study the equation of states of three-dimensional crystalline phases of atomic hydrogen. We show that the results from the CMR method agree much better with the available QMC data in comparison with those from density functional theory and Hartree-Fock calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

First principles assessment of helium trapping in Y{sub 2}TiO{sub 5} in nano-featured ferritic alloys

Nano-scale Y{sub 2}Ti{sub 2}O{sub 7} and Y{sub 2}TiO{sub 5} oxides are the major features that provide high strength and irradiation tolerance in nano-structured ferritic alloys. Here, we employ density functional theory to study helium trapping in Y{sub 2}TiO{sub 5}. The results suggest that helium is more deeply trapped in Y{sub 2}TiO{sub 5} compared to Y{sub 2}Ti{sub 2}O{sub 7}. Helium occupies open channels in Y{sub 2}TiO{sub 5}, where it weakly chemically interacts with neighboring oxygen anions, and results in less volume expansion compared to Y{sub 2}Ti{sub 2}O{sub 7}, reducing strains in the iron matrix. The corresponding helium mobility in these channels is very high. While its ultimate fate is to form oxide/matrix interface bubbles, transient deep trapping of helium in oxides plays a major role in the ability of NFA to manage helium distribution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Changes realized from extended bit-depth and metal artifact reduction in CT

Purpose: High-Z material in computed tomography (CT) yields metal artifacts that degrade image quality and may cause substantial errors in dose calculation. This study couples a metal artifact reduction (MAR) algorithm with enhanced 16-bit depth (vs standard 12-bit) to quantify potential gains in image quality and dosimetry. Methods: Extended CT to electron density (CT-ED) curves were derived from a tissue characterization phantom with titanium and stainless steel inserts scanned at 90-140 kVp for 12- and 16-bit reconstructions. MAR was applied to sinogram data (Brilliance BigBore CT scanner, Philips Healthcare, v.3.5). Monte Carlo simulation (MC-SIM) was performed on a simulated double hip prostheses case (Cerrobend rods embedded in a pelvic phantom) using BEAMnrc/Dosxyz (400 000 0000 histories, 6X, 10 Multiplication-Sign 10 cm{sup 2} beam traversing Cerrobend rod). A phantom study was also conducted using a stainless steel rod embedded in solid water, and dosimetric verification was performed with Gafchromic film analysis (absolute difference and gamma analysis, 2% dose and 2 mm distance to agreement) for plans calculated with Anisotropic Analytic Algorithm (AAA, Eclipse v11.0) to elucidate changes between 12- and 16-bit data. Three patients (bony metastases to the femur and humerus, and a prostate cancer case) with metal implants were reconstructed using both bit depths, with dose calculated using AAA and derived CT-ED curves. Planar dose distributions were assessed via matrix analyses and using gamma criteria of 2%/2 mm. Results: For 12-bit images, CT numbers for titanium and stainless steel saturated at 3071 Hounsfield units (HU), whereas for 16-bit depth, mean CT numbers were much larger (e.g., titanium and stainless steel yielded HU of 8066.5 {+-} 56.6 and 13 588.5 {+-} 198.8 for 16-bit uncorrected scans at 120 kVp, respectively). MC-SIM was well-matched between 12- and 16-bit images except downstream of the Cerrobend rod, where 16-bit dose was {approx}6.4% greater than 12-bit. Absolute film dosimetry in a region downstream of a stainless steel rod revealed that 16-bit calculated dose, with and without MAR, agreed more closely with film results (1%-2% less than film) as compared to 12-bit reconstructions (5.6%-6.5% less than film measurements). Gamma analysis revealed that 16-bit dose calculations were better matched to film results than 12-bit ({approx}10% higher pass rates for 16-bit). Similar results were observed in two patient cases; the largest discrepancy was observed for a femur case where 12-bit doses, both with and without MAR correction, were 6-7 Gy lower ({approx}17%-20% of the prescription dose) as compared to 16-bit dose calculations. However, when beams are not directly traversing metal, such as a prostate cancer case with bilateral hip prostheses; the impact of 16-bit reconstruction was diminished. Conclusions: These results suggest that it may be desirable to implement 16-bit MAR-corrected images for treatment planning purposes, which can provide a more accurate dosimetric approach coupled with improved visualization by suppression of CT artifacts.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2014

Effect of strongly coupled plasma on photoionization cross section

The effect of strongly coupled plasma on the ground state photoionization cross section is studied. In the non relativistic dipole approximation, cross section is evaluated from bound-free transition matrix element. The bound and free state wave functions are obtained by solving the radial Schrodinger equation with appropriate plasma potential. We have used ion sphere potential (ISP) to incorporate the plasma effects in atomic structure calculation. This potential includes the effect of static plasma screening on nuclear charge as well as the effect of confinement due to the neighbouring ions. With ISP, the radial equation is solved using Shooting method approach for hydrogen like ions (Li{sup +2}, C{sup +5}, Al{sup +12}) and lithium like ions (C{sup +3}, O{sup +5}). The effect of strong screening and confinement is manifested as confinement resonances near the ionization threshold for both kinds of ions. The confinement resonances are very much dependent on the edge of the confining potential and die out as the plasma density is increased. Plasma effect also results in appearance of Cooper minimum in lithium like ions, which was not present in case of free lithium like ions. With increasing density the position of Cooper minimum shifts towards higher photoelectron energy. The same behaviour is also true for weakly coupled plasma where plasma effect is modelled by Debye-Huckel potential.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Entanglement entropy and computational complexity of the periodically driven Anderson impurity model

We study the growth of entanglement entropy and bond dimension with time in density matrix renormalization group simulations of the periodically driven single-impurity Anderson model. The growth of entanglement entropy is found to be related to the ordering of the bath orbitals and to the relation of the driving period T to the convergence radius of the Floquet-Magnus expansion. Furthermore, ordering the bath orbitals by their Floquet quasienergy is found to reduce the exponential growth rate of the computation time at intermediate driving periods, suggesting new ways to optimize matrix product state calculations of driven systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2013

Refinement of the Robert-Bonamy Formalism: Considering Effects from the Line Coupling

Since it was developed in 1979, the Robert-Bonamy (RB) formalism has been widely used in calculating pressure broadened half-widths and induced shifts for many molecular systems. However, this formalism contains several approximations whose applicability has not been thoroughly justified. One of them is that lines of interest are well isolated. When these authors developed the formalism, they have relied on this assumption twice. First, in calculating the spectral density F(ω), they have only considered the diagonal matrix elements of the relaxation operator. Due to this simplification, effects from the line mixing are ignored. Second, when they applied the linked cluster theorem to remove the cutoff, they have assumed the matrix elements of the operator exp(-iS(sub 1) - S(sub 2)) can be replaced by the exponential of the matrix elements of -iS(sub 1) - S(sub 2). With this replacement, effects from the line coupling are also ignored. Although both these two simplifications relied on the same approximation, their validity criteria are completely different and the latter is more stringent than the former. As a result, in many cases where the line mixing becomes negligible, significant effects from the line coupling have been completely missed. In the present study, we have developed a new method to evaluate the matrix elements of exp(-iS(sub 1) - S(sub 2)) and have refined the RB formalism such that line coupling can be taken into account. Our numerical calculations of the half-widths for Raman Q lines of the N(sub 2)-N(sub 2) pair have demonstrated that effects from the line coupling are important. In comparison with values derived from the RB formalism, new calculated values for these lines are significantly reduced. A recent study has shown that in comparison with the measurements and the most accurate close coupling calculations, the RB formalism overestimates the half-widths by a large amount. As a result, the refinement of the RB formalism goes in the right direction and these new calculated half-widths become closer to the "true" values.

spectra↗