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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Fully variational incremental CASSCF

We report the complete-active-space self-consistent field (CASSCF) method is a canonical electronic structure theory that holds a central place in conceptualizing and practicing first principles simulations. For application to realistic molecules, however, the CASSCF must be approximated to circumvent its exponentially scaling computational costs. Applying the many-body expansion - also known as the method of increments - to CASSCF (iCASSCF) has been shown to produce a polynomially scaling method that retains much of the accuracy of the parent theory and is capable of treating full valence active spaces. Due to an approximation made in the orbital gradient, the orbital parameters of the original iCASSCF formulation could not be variationally optimized, which limited the accuracy of its nuclear gradient. Herein, a variational iCASSCF is introduced and implemented, where all parameters are fully optimized during energy minimization. This method is able to recover electronic correlations from the full valence space in large systems, produce accurate gradients, and optimize stable geometries as well as transition states. Demonstrations on challenging test cases, such as the oxoMn(salen)Cl complex with 84 electrons in 84 orbitals and the automerization of cyclobutadiene, show that the fully variational iCASSCF is a powerful tool for describing challenging molecular chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Fully quantum calculations of O 2 –N 2 scattering using a new potential energy surface: Collisional perturbations of the oxygen 118 GHz fine structure line

A proper description of the collisional perturbation of the shapes of molecular resonances is important for remote spectroscopic studies of the terrestrial atmosphere. Of particular relevance are the collisions between the $\text{O}_2$ and $\text{N}_2$ molecules—the two most abundant atmospheric species. In this work, we report a new highly accurate $\text{O}_2(\text{X}^3Σ^–_g)–\text{N}_2(\text{X}^1Σ^+_g)$ potential energy surface and use it for performing the first quantum scattering calculations addressing line shapes for this system. We use it to model the shape of the 118 GHz fine structure line in $\text{O}_2$ perturbed by collisions with $\text{N}_2$ molecules, a benchmark system for testing our methodology in the case of an active molecule in a spin triplet state. The calculated collisional broadening of the line agrees well with the available experimental data over a wide temperature range relevant for the terrestrial atmosphere. This work constitutes a step toward populating the spectroscopic databases with ab initio line shape parameters for atmospherically relevant systems.

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

An intermediate model for fitting triplet–triplet annihilation in phosphorescent organic light emitting diode materials

Triplet–triplet annihilation (TTA) is one of the primary contributors to efficiency roll-off and permanent material degradation in phosphorescent organic light-emitting diodes. Here, the two limiting case models typically used to quantify this quenching mechanism are multi-step Dexter and single-step Förster, which, respectively, assume ideal Fickian diffusion or perfect trapping of triplet excitons. For device-relevant guest doping levels (typically 5–12 vol. %), both significant diffusion of excitons and trapping due to spatial and energetic disorder exist, so neither conventional model fits experimental data well. We develop and validate an intermediate TTA model, which is a weighted average of the limiting cases of pure radiative decay (no TTA) and multi-step Dexter based TTA that returns an effective TTA rate constant and a parameter quantifying the portion of well-isolated excitons. Kinetic Monte-Carlo simulations and time-resolved photoluminescence measurements of an archetype host–guest system demonstrate that our intermediate model provides significantly improved fits with more realistic physical values, is more robust to variations in experimental conditions, and provides an analysis framework for the effects of trapping on TTA.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Spin selective charge recombination in chiral donor-bridge-acceptor triads

In this paper, we outline a physically motivated framework for describing spin-selective recombination processes in chiral systems, from which we derive spin-selective reaction operators for recombination reactions of donor–bridge–acceptor molecules, where the electron transfer is mediated by chirality and spin–orbit coupling. In general, the recombination process is selective only for spin-coherence between singlet and triplet states, and it is not, in general, selective for spin polarization. We find that spin polarization selectivity only arises in hopping-mediated electron transfer. We describe how this effective spin-polarization selectivity is a consequence of spin-polarization generated transiently in the intermediate state. Furthermore, the recombination process also augments the coherent spin dynamics of the charge separated state, which is found to have a significant effect on the recombination dynamics and to destroy any long-lived spin polarization. Although we only consider a simple donor–bridge–acceptor system, the framework we present here can be straightforwardly extended to describe spin-selective recombination processes in more complex systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spatially inhomogeneous superconductivity in UTe 2

The newly discovered superconductor UTe 2 is a strong contender for a topological spin-triplet state wherein a multicomponent order parameter arises from two nearly degenerate superconducting states. A key issue is whether both of these states intrinsically exist at ambient pressure. Through thermal expansion and calorimetry, we show that UTe 2 at ambient conditions exhibits two detectable transitions only in some samples, and the size of the thermal expansion jump at each transition varies when the measurement is performed in different regions of the sample. This result indicates that the two transitions arise from two spatially separated regions that are inhomogeneously mixed throughout the volume of the sample, each with a discrete superconducting transition temperature (T c ). Notably, samples with higher T c only show a single transition at ambient pressure. Above 0.3 GPa, however, two transitions are invariably observed in ac calorimetry. Our results not only point to a nearly vertical line (constant pressure) in the pressure-temperature phase diagram but also provide a consistent scenario for the sample dependence of UTe 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1970

The perturbation spectrum of CO

Perturbation rotational levels in triplet states of CO emission spectra attributed to resonance fluorescence process involving optically forbidden transitions

Black, G.↗
NASA NTRS1972

The IR emission spectrum of N2 excited under auroral conditions.

Recently determined experimental and theoretical cross sections for electron impact excitation of six triplet states of N2 (A, B, W, C, E, D) have been utilized to predict the absolute IR volume emission rates from N2 under nighttime auroral conditions. Secondary electron fluxes appropriate to an IBC II normal aurora were used in the calculations. The cascade contributions coupling the various electronic states were included as well as the most important quenching processes. The results indicate that the B yields reversibly A and W yields reversibly B cascade processes, which are important in the population of the A, B, and W states, produce appreciable radiation in the 1- to 5-micron wavelength region.

Cartwright, D. C.↗
NASA NTRS1976

Coordinated analysis of various auroral measurements made during NASA's 1968 and 1969 airborne auroral expeditions

Auroral optical measurements made aboard NASA's CV 990 were analyzed. The measurements analyzed form a small part of extensive spectroscopic, photometric and photographic data gathered during the 1968 and 1969 Airborne Auroral Expeditions. Simultaneous particle measurements from ESRO IA satellite were used in the analysis. Information about magnetospheric boundaries, interaction between magnetosheath particles and the terrestrial ionosphere, the polar bulge in helium abundance and excitation mechanisms of the triplet state of atmospheric N2 in auroras was obtained. Further analysis of the data is required to elucidate the relation between 3466 and 5200 A emissions of NI and the excitation of 3726-3729 A emissions from atomic oxygen ions in auroras.

Sivjee, G. G.↗
NASA NTRS1975

Diffusion in mixed solvents. II - The heat of mixing parameter

Correlation of second-order rate constants for many reactions involving electron transfer between organic molecules, solvated electron reactions, iodine diffusion coefficients, and triplet state electron transfer reactions has been made with the heat of mixing parameter (HMP) for the aqueous binary solvent systems. The aqueous binary solvents studied are those containing methanol or ethanol (type I solvent); 1-propanol or tert-butyl alcohol (type II solvent); or sucrose or glycerol (type III solvent). A plot of the HMP vs. the diffusion parameter for each reaction yields superimposable curves for these reactions in a particular solvent mixture over the entire solvent mixture range, irrespective of the value of the reaction's rate constant or diffusion coefficient in water.

Carapellucci, P. A.↗
NASA NTRS1982

Fluorescence yields from photodissociation of OCS at 1060-1240 A

The cross sections for the production of fluorescence (3000-8000 A) from excited photofragments of OCS were determined in order to gain a better understanding of the role of carbonyl sulfide in interstellar photochemistry. Synchrotron radiation was used as the light source for the measurements in the 1060-1240 A region, as it is suitable for measuring the absorption cross section in the structured region. It was found that the quantum yields for the production of various CO triplet states are less than 1.5% at the observed excitation photon wavelengths.

Lee, L. C.↗
NASA NTRS1983

The gamma-ray spectrum of the Galactic-center region

The HEAO-3 High Resolution Gamma-Ray Spectrometer observed the Galactic center region in fall 1979 and in the spring of 1980. Variation of the positron annihilation line at 511 keV has been reported previously. The fall 1979 observations show a significant high-energy continuum at energies above 511 keV. The intensity of a possible positronium triplet-state continuum is found to be less than that expected for direct positron annihilation and positronium decay in an ionized, warm (T approximately equal to or less than 10 to the 5th K) plasma. Depending on assumption for the shape of the high-energy continuum spectrum, positronium fractions between 0.0 and 0.75 (at 90 percent statistical confidence level) are consistent with the observations.

Riegler, G. R.↗
NASA NTRS1989

Measurement Of Molecular Mobilities Of Polymers

New molecular-probe technique used to measure molecular mobility of polymer. Method based on use of time-resolved electron-spin resonance (ESR) spectroscopy to monitor decay of transient nutation amplitudes from photoexcited triplet states of probe molecules with which polymer is doped. The higher molecular mobility of polymer matrix, the faster nutation amplitudes of the probe molecules decay.

Kim, Soon Sam↗
NASA NTRS1990

Theoretical study of the spectroscopy of ZrO

The absorption bands of ZrO have been observed in stars, particularly S stars. Here, theoretical transition probabilities are presented for the dipole-allowed transitions between the six lowest singlet and triplet states of ZrO. The results should be sufficiently reliable to provide opacity data for use in modeling stellar atmospheres. The theoretical radiative lifetime for the e 3Pi state is less than the experimental value as measured by the decay of resonant fluorescence. However, the theoretical electronic transition moments for the gamma system and the B 1Pi - X 1Sigma(+) system are much smaller than those deduced from emission studies. The calculated lifetime for the C 1Sigma(+) state is in excellent agreement with the laser-induced fluorescence studies. The as yet unobserved E 1Phi - A 1Delta band system is found to be relatively strong.

Langhoff, Stephen R.↗
NASA NTRS1992

The complete UV spectrum of SO2 and electron impact. II - The middle ultraviolet spectrum

Measurements of the middle ultraviolet (MUV) electron impact induced fluorescence spectrum of SO2 from 200 to 430 nm in a crossed beam experiment are reported. The spectrum is dominated by two features at the experimental resolution of 0.5 nm; these two features are referred to as MUV1 and MUV2. MUV1 is the SO band system extending from 240 to 265 nm produced by dissociative excitation. MUV2 is a blend of the SO2 and SO2(+) molecular band systems in the range 264-430 nm. The excitation function measurements of MUV2 indicate that low-energy electrons effectively prepare SO2 in one or more electronically excited triplet states that involve the SO2 state by direct excitation and/or cascading. The peak cross section for MUV1 occurs at 20 eV with a value of 25.0 +/-5.5 x 10 exp -19 sq cm. The peak cross section for MUV2 arises at 9 eV with a value of 368 +/-81 x 10 exp -19 sq cm. The laboratory results provide a plausible explanation of the Io auroral hot spots observed by Voyager 2.

Ajello, Joseph M.↗
NASA NTRS1992

Photodissociation of CH2. I - Potential energy surfaces of the dissociation into CH and H

The possible photodissociation pathways of the CH2 radical are studied using ab initio multireference configuration-interaction methods, and accurate photodissociation cross sections and branching ratios for the production of CH + H and C + H2 are obtained. Potential energy surfaces were calculated using the Wuppertal-Bonn self-consistent field plus a multireference single and double-excitation configuration interaction package of programs. Two-dimensional potential energy surfaces of the ten lowest triplet states correlating with the seven lowest states of CH were calculated as functions of bond angle and one C-H bond distance, keeping the other C-H bond distance fixed at the equilibrium CH2 value.

Bearda, Robert A.↗
NASA NTRS1996

On the Photoelectron Spectra of Li4

The most stable structure for Li4(-) is found to be the rhombus. Electron detachment from this structure does not seem able to fully explain the photoelectron spectra. The computed results are consistent with those Rao, Jena, and Ray who have proposed that the experimental spectra consists of a superposition of detachment from the Li4(-) rhombus and tetrahedron, forming the singlet and triplet states of Li4, respectively.

Bauschlicher, Charles W., Jr.↗