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At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Transport properties of monatomic carbon

Transport collision integrals for each of the 18 molecular C2 states that dissociate into ground state carbon atoms are presented. The integrals are obtained by fitting two-body semiempirical interaction potentials, for which the collision integrals are tabulated, to experimental and/or accurate theoretical calculations for each of these states. The collision integrals are applied to calculate the diffusion coefficient, viscosity, and translational contribution to the thermal conductivity of monatomic carbon at 1-atm pressure from 1000 K to 25,000 K. Because of ablation injection, monatomic carbon is an important flow field constituent of ablative flow during planetary entry, and knowledge of the transport properties for carbon species is required for calculating the flow field properties and surface heating.

Biolsi, L.↗
NASA NTRS1983

Monodeuterated methane in the outer solar system. I Spectroscopic analysis of the bands at 1.55 and 1.95 microns

The analysis of the near-infrared spectrum of monodeuterated methane (CH3D) near 6400/cm and 5100/cm is presented. Three new parallel bands which have locally perturbed upper states connecting with the ground state are identified, and approximate rotational constants are derived. The band centered near 6425/cm and the 9613 A band previously analyzed by Lutz, Danehy, and Ramsay (1978) are found to form an apparent vibrational progression with the nu2 fundamental at 2200/cm, and vibrational assignments of 3nu2 and 5nu2, respectively, are proposed. Detailed comparison of the rotational constants of the states involved is shown to support these assignments.

Lutz, B. L.↗
NASA NTRS1985

The internal state distribution of CN radicals produced in the photolysis of HC2CN and CH3CN

The energy partitioning in CN radicals produced by the vacuum ultraviolet photodissociation of HC2CN and CH3CN is studied by means of laser-induced fluorescence of the B-X transition. Experiments are performed in two collision regimes: (1) in the low-collision number regime, the energy partitioning in CN(X) is measured; (2) in the high-collision number regime, the formation of CN(A) is monitored. It is shown that photodissociation of HC2CN in its linear predissociative 1Sigma(+) state produces predominantly ground-state CN in rotationally and vibrationally excited states. The vibrational population ratios and the temperatures computed from a Boltzmann fit of the rotational levels are given in a table. The excitation of CH3CN produces CN radicals almost entirely in the first excited A-state with vibrational excitation.

Cody, R. J.↗
NASA NTRS1988

The computed spectrum of AlC

The low-lying (up to about 40,000/cm) doublet and quartet states of AlC have been studied at the CASSCF and MRCI levels of theory. The bonding in the X4Sigma(-) state is shown to involve three one-electron bonds. The first excited state, a 2Pi, lies about 8700/cm higher and like the X4Sigma(-) state is derived from ground state Al and C, but has a two-electron pi bond leading to a much shorter bond length.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

The OI 989 and 1173 A multiplets in the dayglow

Sounding rocket measurements of the O-I 989-A dayglow obtained in 1978, 1980, and 1985 are discussed. The 989-A intensity and multiplet ratios are consistent with total branching losses (to atomic states other than the ground state) of 1.5-4 x 10 to the -4th. It is found that the 1173/989 intensity ratio is dependent only on the 1173/989 branching ratio and the atomic oxygen concentration when viewing upward from rocket altitudes.

Morrison, M. D.↗
NASA NTRS1991

Theoretical study of the spectroscopy of B2

A study is made of the singlet, triplet, and quintet states of B2 below 45,000/cm at the multireference configuration-interaction level. The stronger bonding in B2, as compared with Al2, manifests itself in the potential energy curves. In B2, five of the six states dissociating to the ground state atoms are bound, compared with only two for Al2. Radiative lifetimes are reported for the lowest vibrational level of many of the bound triplet states of B2.

Langhoff, Stephen R.↗
NASA NTRS1994

Causality problems for Fermi's two-atom system

Let A and B be two atoms or, more generally, a 'source' and a 'detector' separated by some distance R. At t = 0 A is in an excited state, B in its ground state, and no photons are present. A theorem is proved that in contrast to Einstein causality and finite signal velocity the excitation probability of B is nonzero immediately after t = 0. Implications are discussed.

Hegerfeldt, Gerhard C.↗
NASA NTRS2005

Measurements of Line Positions and Strengths of HD O-18 and D2 O-18 in the 2500-4280 cm(exp -1) Region

Measurements of line positions and strengths of D2 O-18 and HD O-18 were obtained with a Fourier transform spectrometer. The data were analyzed to obtain energy levels of the (100), (020), and (001) vibrational states of HD O-18 and the (001) and (011) states of D2 O-18 and the vibrational bands of these states connected to the ground state covered the spectral region from 2500 to 4278 cm(exp -1). 456 absorption lines of D2 O-18 and 856 lines of HD O-18 were assigned from the spectra. The measurements were of oxygen-18 enriched samples of deuterated water vapor and the spectra also contained features of HD O-16, D2 O-16, H2 O-16, H2 O-17 and H2 O-18 of which several were used as frequency calibration standards.

Fourier transform spectrometer (FTS)↗
DOE OSTI2025

Ground and excited state properties of ThBe and AcBe

In this work, the ground and excited states of ThBe and AcBe were investigated by performing high-level multireference and single-reference coupled-cluster quantum chemical calculations with large correlation consistent basis sets. Full potential energy curves (PECs), chemical bonding patterns, energetics, spectroscopic parameters (T e , r e , ω e , and ω e x e ), and spin–orbit effects of 13 and 8 electronic states of ThBe and AcBe, respectively, are reported. The ground electronic states of ThBe and AcBe are single-reference 1 3 Σ − (1σ 2 2σ 2 1π 2 ) and 1 2 Π (1σ 2 2σ 2 1π 1 ), respectively, and originate from their corresponding ground state fragments. The chemical bonding of ThBe (1 3 Σ − ) and AcBe (1 2 Π) are π-dative in character and are formed by d-electron transfers from Th/Ac to the empty 2p x and 2p y of the Be atom. The electron populations of the f-orbitals of both ThBe (1 3 Σ − ) and AcBe (1 2 Π) are minor which exhibit their “transition-metal-like” nature. The estimated bond energies of the spin–orbit ground states of ThBe (1 3 Σ − 0+ ) and AcBe (1 2 Π 1/2 ) are 12.79 and 11.02 kcal mol −1 , respectively. Finally, the bond energy of ThBe was used to estimate its heat of formation ΔH 0 f (298 K) of 869.61 ± 6 kJ mol −1 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Analysis of the 18 F g,m (d,p) 19 F reactions in the rotational model

Spectroscopic strengths for the 18 F g , m ( d , p ) F 19 reactions to members of the ground-state band in F 19 are interpreted in the rotational model. The analysis considers two different coupling schemes, namely, the strong and decoupled limits of the particle rotor model to describe the ground and isomeric states of F 18 , as well as the transitions to the ground-state band in F 19 . Our results, obtained using Nilsson amplitudes for the neutron levels 1 2 [ 220 ] , 3 2 [ 211 ] , and 5 2 [ 202 ] calculated at a deformation ε 2 = 0.32 are in agreement with the measurements and USDB shell-model calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Examination of the inversion of isobaric analogue states in mirror nuclei

A recent study by Hoff and collaborators [Nature (London) 580, 52 (2020)] presented evidence that the ground-state spin of [Math Processing Error] is different from that of its mirror, [Math Processing Error], likely due to an inversion of the ground- and first-excited states. Here, we assess the likelihood of such an inversion arising from normal isospin-symmetry breaking and, more broadly, whether such phenomena challenge our understanding of charge-symmetry-breaking forces in atomic nuclei. By placing the result within the context of previous experimental and theoretical work we demonstrate that this inversion lies entirely within the bounds of normal isospin-symmetry-breaking behavior. We further note that, in the context of isospin, neither level inversions nor the nuclear ground state hold any special significance.

59 ≤ A ≤ 89↗
NASA NTRS2000

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Bridged Compounds/chemistry↗
DOE OSTI2022

Magnetic exchange interactions in binuclear and tetranuclear iron(III) complexes described by spin‐flip DFT and Heisenberg effective Hamiltonians

Abstract Low‐energy spectra of single‐molecule magnets (SMMs) are often described by Heisenberg Hamiltonians. Within this formalism, exchange interactions between magnetic centers determine the ground‐state multiplicity and energy separation between the ground and excited states. In this contribution, we extract exchange coupling constants ( J ) for a set of iron (III) binuclear and tetranuclear complexes from all‐electron calculations using non‐collinear spin‐flip time‐dependent density functional theory (NC‐SF‐TDDFT). For 12 binuclear complexes with J ‐values ranging from −6 to −132 cm −1 , our benchmark calculations using the short‐range hybrid ω PBEh functional and 6‐31G(d,p) basis set agree well with the experimentally derived values (mean absolute error of 4.7 cm −1 ). For the tetranuclear SMMs, the computed J constants are within 6 cm −1 from the experimentally derived values. We explore the range of applicability of the Heisenberg model by analyzing bonding patterns in these Fe(III) complexes using natural orbitals (NO), their occupations, and the number of effectively unpaired electrons. The results illustrate the efficiency of the spin‐flip protocol for computing the exchange couplings and the utility of the NO analysis in assessing the validity of effective spin Hamiltonians.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular Geometry and Electronic Structure of Copper Corroles

Copper corroles are known for their unique multiconfigurational electronic structures in the ground state, which arise from the transfer of electrons from the π orbitals of the corrole to the d-orbital of copper. While density functional theory (DFT) provides reasonably good molecular geometries, the determination of the ground spin state and the associated energetics is heavily influenced by functional choice, particularly the percentage of the Hartree–Fock exchange. Using extended multireference perturbation theory methods (XMS-CASPT2), the functional choice can be assessed. The molecular geometries and electronic structures of both the unsubstituted and the meso-triphenyl copper corroles were investigated. A minimal active space was employed for structural characterization, while larger active spaces are required to examine the electronic structure. The XMS-CASPT2 investigations conclusively identify the ground electronic state as a multiconfigurational singlet (S o ) with three dominant electronic configurations in its lowest energy and characteristic saddled structure. In contrast, the planar geometry corresponds to the triplet state (T o ), which is approximately 5 kcal/mol higher in energy compared to the S o state for both the bare and substituted copper corroles. Notably, the planarity of the T o geometry is reduced in the substituted corrole compared with that in the unsubstituted one. By analyzing the potential energy surface (PES) between the S o and T o geometries using XMS-CASPT2, the multiconfigurational electronic structure is shown to transition toward a single electron configuration as the saddling angle decreases (i.e., as one approaches the planar geometry). Despite the ability of the functionals to reproduce the minimum energy structures, only the TPSSh-D 3 PES is reasonably close to the XMS-CASPT2 surface. Significant deviations along the PES are observed with other functionals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗