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At least 55 records · Page 3

Theoretical study of the dipole moments of selected alkaline-earth halides

Ab initio calculations at the self-consistent-field (SCF), singles-plus-doubles configuration-interaction (SDCI), and coupled-pair functional (CPF) level, are reported for the dipole moments and dipole derivatives of the X2Sigma(+) ground states of BeF, BeCl, MgF, MgCl, CaF, CaCl, and SrF. For comparison, analogous calculations are performed for the X1Sigma(+) state of KCl. The CPF results are found to be in remarkably better agreement with experiment than are the SCF and SDCI results. Apparently higher excitations are required to properly describe the radial extent along the bond axis of the remaining valence electron on the alkaline-earth metal.

Langhoff, S. R.↗

Theoretical study of the X 2Pi and A 2Sigma(+) states of CuO and CuS

Theoretical spectroscopic constants and dipole moments are determined for the X 2Pi and A 2Sigma(+) states of CuO and CuS, using extended Gaussian basis sets and incorporating correlation using both configuration interaction (CI) and coupled pair (CPF) methods. Relativistic corrections (Darwin plus mass velocity), included using first-order perturbation theory, are found to be relatively small. At the CPF level, significant configuration mixing with the 3d(9)4s(1) occupation occurs for both states, resulting in some bond shortening and a significant increase in the dissociation energy. The best spectroscopic parameters are in excellent agreement with experiment for both CuO and CuS. In analogy with CuO, CuS is predicted to have a yet unobserved 2Sigma(+) state near 10,000 per cm.

Langhoff, S. R.↗

Theoretical study of the electric dipole moment function of the ClO molecule

The potential energy function and electric dipole moment function (EDMF) are computed for ClO X 2Pi using several different techniques to include electron correlation. The EDMF is used to compute Einstein coefficients, vibrational lifetimes, and dipole moments in higher vibrational levels. The band strength of the 1-0 fundamental transition is computed to be 12 + or - 2 per sq cm atm determined from infrared heterodyne spectroscopy. The theoretical methods used include SCF, CASSCF, multireference singles plus doubles configuration interaction (MRCI) and contracted CI, coupled pair functional (CPF), and a modified version of the CPF method. The results obtained using the different methods are critically compared.

Pettersson, L. G. M.↗

Theoretical study of the low-lying electronic states of ZnO and ZnS

Theoretical spectroscopic constants and dipole moments are determined for the 1 Sigma(+), 1,3 Pi, and 3 Sigma(+) states of ZnO and ZnS, using extended Gaussian basis sets and incorporating correlation using both configuration-interaction and coupled pair (CPF) methods. Relativistic corrections (Darwin plus mass velocity), included using first-order perturbation theory, are relatively small. At the CPF level, both ZnO and ZnS have 1 Sigma(+) ground states, with the 3 Pi state lying 209 and 2075/cm higher, respectively. The 3 Sigma(+) state lies about 1.5 eV higher in ZnO and 2.1 eV higher in ZnS. The 1,3 Pi states are relatively close together since the exchange splitting is small with the sigma electron localized on Zn and the pi electron on oxygen (or sulfur).

Bauschlicher, C. W., Jr.↗

Theoretical spectroscopic parameters for the low-lying states of the second-row transition metal hydrides

A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.

Langhoff, Stephen R.↗

Full CI studies of the collinear transition state for the reaction F + H2 yields HF + H

Full CI calculations on the collinear transition state for the reaction F + H2 yields HF + H are reported. The full CI results are compared with those obtained from single-reference and multireference CI calculations and from single-reference CPF calculations. In general, only those methods which attempt to account for the effects of higher excitations, such as CPF or CI plus the Davidson correction, yield a transition-state location and barrier height in good agreement with the full CI. In an extended basis, the effect of higher excitations is estimated to lower the barrier by as much as 1.5 kcal/mol; such an effect would essentially eliminate the present discrepancy between theory and experiment.

Bauschlicher, Charles W., Jr.↗

Full CI benchmark calculations on N2, NO, and O2 - A comparison of methods for describing multiple bonds

Full configuration interaction (CI) calculations on the ground states of N2, NO, and O2 using a DZP Gaussian basis are compared with single-reference SDCI and coupled pair approaches (CPF), as well as with CASSCF multireference CI approaches. The CASSCF/MRCI technique is found to describe multiple bonds as well as single bonds. Although the coupled pair functional approach gave chemical accuracy (1 kcal/mol) for bonds involving hydrogen, larger errors occur in the CPF approach for the multiple bonded systems considered here. CI studies on the 1Sigma(g +) state of N2, including all single, double, triple, and quadruple excitations show that triple excitations are very important for the multiple bond case, and accounts for most of the deficiency in the coupled pair functional methods.

Bauschlicher, Charles W., Jr.↗

Theoretical study of the dipole moment function of OH(X 2Pi)

A complete theoretical electric dipole moment function mu(r) is computed for OH(X 2Pi) at the full configuration-interaction (FCI) level for DZP + diffuse Gaussian basis set. The energy and dipole moment are also determined with 2d functions on oxygen at seven r values. The following methods are compared to the FCI for both the oxygen 1d and 2d basis sets: single-reference singles-plus-doubles configuration interaction (SDCI), SDCI with Davidson's correction, the coupled pair functional approach (CPF) and a modified form of CPF, CASSCF, and CASSCF-MRSDCI, and the external contracted CI(CCI) method. The dipole moments are evaluated both as an expectation value and by finite-field methods. The results support the superiority of evaluating the dipole moment as an energy derivative rather than as an expectation value.

Langhoff, Stephen R.↗

Full configuration interaction benchmark calculations for TiH

Full configuration interaction (FCI) results for the 3F and 5F states of Ti and the 4Phi and 2Delta states of TiH are presented. While the coupled pair functional (CPF) or modified CPF approaches are found to work well for the 4Phi state of TiH, they do not perform as well for the 2Delta state. Although for mu, the CASSCF/MRCI methods do well for the 2Delta state, when the active space is expanded outside the normal valence definition, the dipole moment is only brought into agreement with the FCI results by natural orbital iterations.

Bauschlicher, Charles W., Jr.↗

On the electronic structure and spectrum of CuF2 and CuCl2

Results are reported from SDCI and CPF ab initio computations for the ground and low-lying states of CuF2 and CuCl2. A large Gaussian basis set with functions up to the g level is employed, and the results are presented in tables and characterized in detail. Particular attention is given to the bond distances and force constants for the ligand-field states and the bond distances for the charge-transfer states. Good agreement is obtained between the CPF and SDCI values and with published experimental data.

Bauschlicher, Charles W., Jr.↗

Algebraic grid generation with control points

The control-point form (CPF) formulation is an algebraically defined class of coordinate transformations by means of which the interior form of the coordinates can be manipulated in the local fashion, and any boundary can be either specified or manipulated in a similar manner. Currently, the most intense activity involving CPF is with such graphic interactive codes as TurboI and TurboT, for which detailed illustrative examples are given; these have furnished experience on whose basis future interactive strategies can be developed.

Eiseman, Peter R.↗

Theoretical Study of the Electric Dipole Moment Function of the CIO Molecule

The potential energy function and electric dipole moment function (EDMF) are computed for CIO Chi(sup 2)Pi using several different techniques to include electron correlation. The EDMF is used to compute Einstein coefficients, vibrational lifetimes, and dipole moments in higher vibrational levels. Remaining questions concerning the position of the maximum of the EDMF may be resolved through experimental measurement of dipole moments of higher vibrational levels. The band strength of the 1-0 fundamental transition is computed to be 12 +/- 2 /sq cm atm in good agreement with three experimental values, but larger than a recent value of 5 /sq cm atm determined from infrared heterodyne spectroscopy. The theoretical methods used include SCF, CASSCF, multireference singles plus doubles configuration interaction (MRCI) and contracted CI, coupled pair functional (CPF), and a modified version of the CPF method. The results obtained using the different methods are critically compared.

Pettersson, Lars G. M.↗

Spectral Polarization Distribution Models (PDMs) for NASA CLARREO Pathfinder’s Inter-Calibration Applications

Solar radiation scattered by Earth surfaces of various scene types such as oceans, deserts, tree leaves etc and atmospheric molecules and particles is polarized and the amount of polarization depends on the surface composition and particle physical properties. This can be a source of measurement errors in satellite data if a non-polarimetric radiometric sensor is sensitive to the polarization state of light. To obtain highly accurate spectral solar radiation data from the Earth-atmosphere system for the space-borne inter-calibration studies as proposed in NASA's Climate Absolute Radiance and Refractivity Observatory (CLARREO) mission and the CLARREO Pathfinder (CPF) mission, the spectral polarization state of the reflected solar light at the top of atmosphere (TOA) must be known with sufficient accuracy. The degree of polarization (DOP) and the angle of linear polarization (AOLP) of the light at the TOA as functions of incident and viewing geometry and scene type construct the Polarization Distribution Models (PDMs) for correction of polarization-induced error of satellite data. In this work, algorithms for modeling the spectral polarization state of reflected sunlight from various types of Earth, including oceans, deserts, vegetated land surfaces and these scene types with all kinds of clouds, are developed. By comparing the model results with the PARASOL satellite data, our numerical results demonstrate that the model can provide a reliable approach for making the spectral PDMs for wavelengths between 320 and 2300 nm for satellite inter-calibration applications as proposed in the CLARREO and the CLARREO CPF missions.

Sun, Wenbo↗

Principal Component-Based Radiative Transfer Model (PCRTM) for Hyperspectral Remote Sensors for UV, VVIS, NIR, IR, and FIR Spectral Regions

Fast and accurate radiative transfer models are needed to efficiently process satellite hyperspectral remote sensors. We have developed a Principal Component-based radiative transfer model (PCRTM) which can simulate TOA radiance or reflectance spectra in the cloudy atmosphere for far IR, IR, NIR, VIS, and UV spectral regions quickly and accurately. Multi-scattering of multiple layers of clouds/aerosols is included in the model. Polarization components can also be calculated. The computation speed is 3 to 4 orders of magnitude faster than MODTRAN5, LBLRTM, and VLIDORT. The PCRTM calculated radiance spectra agree with reference RTM calculated radiance spectra very well (0.03 K in IR and 0.05% in solar). Comparisons of the PCRTM model calculations with observed AIRS, CrIS, IASI, NAST-I, and SCIAMACHY data will be presented. The solar-PCRTM has been developed for CLARREO PathFinder (CPF) and has been extensively used for CPF science algorithms. The PCRTM can also be used for many current and future NASA future missions such as EMIT, SBG, TEMPO, and PACE.

pcrtm↗

Earth Science Data Processing With Nextflow

Earth science data processing tasks present many challenges. These tasks often process large input datasets and require scores of CPU-hours to generate results. All but the simplest tasks will be decomposed into a series of computational or data manipulation steps, also known as a scientific workflow. In order to reduce the burden of orchestrating and running the dependent processing steps, a workflow execution engine is required. This poster describes the lessons learned by the CLARREO Pathfinder (CPF) team while developing multiple scientific workflows and utilizing the open-source Nextflow engine to execute them in a cloud computing environment. The Nextflow engine is designed with the following stated goals: first, the engine does not dictate how individual steps in the task are implemented (i.e. it is language and interface agnostic); second, the engine supports easy configuration and modularity at the workflow level so that others can easily execute our workflows to reproduce results; lastly, the engine eases development by transparently scaling execution from local to remote environments. Nextflow was developed for the bioinformatics domain but is a good fit for other scientific workflows where the overall task is well-described by a dataflow diagram. The CPF team has developed Nextflow pipelines (i.e. scientific workflows) to simulate CLARREO radiance, generate large look-up tables for inter-calibration algorithms, and generate L4 intercalibration data products. These pipelines consume from single-digits to hundreds of thousands of CPU-hours. In the development and evolution of these pipelines we have discovered many design patterns, pitfalls, and solutions to common problems. Our goal is to demonstrate important aspects of how to design, implement, run, and ultimately share Nextflow pipelines in the domain of Earth science.

Aron D Bartle↗

The HySICS Pointing System: Precision Pointing of CLARREO Pathfinder from the ISS

The CLARREO (Climate Absolute Radiance and Refractivity Observatory) Pathfinder (CPF) mission will measure Earth-reflected sunlight with unparalleled accuracy over existing reflected solar (RS) sensors and will also serve as an on-orbit inter-calibration reference to other orbiting sensors. In order to achieve these goals, the HySICS (HyperSpectral Imager for Climate Science) instrument will need to be pointed at a diverse set of targets including: nadir earth, co-aligned earth scans with other orbiting sensors, the Sun, and the Moon. The HySICS Pointing System (HPS) was developed to provide independent pointing at these targets from its mounting location on the ISS. This paper is focused on the HPS and describes: an overview of the CPF mission, an overview of the HPS requirements, the HPS hardware architecture, the various pointing modes that allow the HPS to point at its targets, challenges associated with performing this mission on the ISS, test results from subsystem-level HPS testing, and finally lessons learned that pertain to algorithm/software development and to the benefits of reusing pointing control hardware/architecture from the TSIS-1 mission that also has a 2-axis pointing system on the ISS from the development process.

orbit↗

A Principal-Component-Based Radiative Transfer Model (PCRTM) for Hyperspectral Shortwave and Longwave Satellite Sensors and Its Applications

The radiative transfer model (RTM) or forward model is an essential component in satellite remote sensing. For modern hyperspectral remote sensors, fast and accurate RTMs are needed due to a large number of spectral dimensions and high spatial resolutions. We will describe a Principal Component-based radiative transfer model (PCRTM) which can simulate the top-of-atmosphere (TOA) radiance or reflectance spectra 250 nm to 2000 micrometers quickly and accurately. The PCRTM has been demonstrated to be extremely accurate, compared to the line-by-line RTM benchmarks, and the former is several orders more computationally efficient than the latter. We will demonstrate how the PCRTM and the associated inversion algorithms are used to infer atmospheric temperature, moisture, and trace gas profiles, as well as cloud and surface properties from hyperspectral IR sounders such as Atomspheric Infrared Souder (AIRS) and Cross-track Infrared Sounder (CrIS). High-quality climate records for a 20-year duration have been derived from these IR hyperspectral data. Finally, we will show some examples of using PCRTM to retrieve cloud properties from Earth Surface Mineral Dust Source Investigation (EMIT) and its applicability of PCRTM to future missions such as the CLARREO (Climate Absolute Radiance and Refractivity Observatory) Pathfinder (CPF) CPF and the Surface Biology and Geology (SBG).

Xu Liu↗

CLARREO Pathfinder Solar Diffuser Calibration Progress

Climate Absolute Radiance and Refractivity Observatory (CLARREO) Pathfinder (CPF) mission’s Hyperspectral Imager for Climate Science (HySICS) instrument’s transmissive flight diffuser calibration is presented. The absolute Bidirectional Transmittance Distribution Function (BTDF) measurement of the transmissive diffuser is needed to calculate the instrument’s absolute efficiency. Along with a known solar irradiance source such as Total Solar Irradiance Sensor (TSIS), it can provide an absolute irradiance measurement path on orbit, with NIST traceability. This provides an additional path for CPF to cross compare with other on orbit sensors’ measurement such as Visible-Infrared Imaging Radiometer Suite (VIIRS), Clouds and the Earth’s Radiant Energy System (CERES). The flight diffuser was calibrated at NASA’s Goddard Space Flight Center (GSFC) using the Facility’s Optical Scatterometer.

Bidirectional Transmittance Distribution Function↗