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At least 1,225 records · Page 68
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Quantum simulation of charge and exciton transfer in multi-mode models using engineered reservoirs

Quantum simulation enables studies of open-system dynamics in non-perturbative regimes by programming electronic, vibrational, and environmental interactions on comparable energy scales. Trapped ions offer this capability, combining spins, phonons, and tunable dissipation on one platform. We demonstrate an open-system quantum simulation of charge and exciton transfer in a multi-mode linear vibronic coupling model. Using tailored spin-phonon interactions with reservoir engineering, we emulate a system with two dissipative vibrational modes coupled to donor and acceptor sites and track its non-equilibrium dynamics. We continuously tune the system from the charge transfer regime to the vibrationally assisted exciton transfer regime and find that degenerate modes enhance transfer rates at large energy gaps, while non-degenerate modes activate pathways that reduce the energy-gap dependence. Thus, the presence of one additional vibration introduces interfering pathways and reshapes non-perturbative excitation transfer. Our results establish a scalable, hardware-efficient route to simulate vibronic processes with engineered environments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Fabricating Graphene Oxide/h-BN Metal Insulator Semiconductor Diodes by Nanosecond Laser Irradiation

To employ graphene’s rapid conduction in 2D devices, a heterostructure with a broad bandgap dielectric that is free of traps is required. Within this paradigm, h-BN is a good candidate because of its graphene-like structure and ultrawide bandgap. We show how to make such a heterostructure by irradiating alternating layers of a-C and a-BN film with a nanosecond excimer laser, melting and zone-refining constituent layers in the process. With Raman spectroscopy and ToF-SIMS analyses, we demonstrate this localized zone-refining into phase-pure h-BN and rGO films with distinct Raman vibrational modes and SIMS profile flattening after laser irradiation. Furthermore, in comparing laser-irradiated rGO-Si MS and rGO/h-BN/Si MIS diodes, the MIS diodes exhibit an increased turn-on voltage (4.4 V) and low leakage current. The MIS diode I-V characteristics reveal direct tunneling conduction under low bias and Fowler-Nordheim tunneling in the high-voltage regime, turning the MIS diode ON with improved rectification and current flow. This study sheds light on the nonequilibrium approaches to engineering h-BN and graphene heterostructures for ultrathin field effect transistor device development.

2D materials↗
NASA NTRS1995

The Ultraviolet Spectrum of the Jovian Dayglow

The ultraviolet spectra of molecular hydrogen H2 and HD due to solar fluorescence and photoelectron excitation are calculated and compared with the Jovian equatorial dayglow spectrum measured at 3 A resolution at solar maximum. The dayglow emission is accounted for in both brightness and spectral shape by the solar fluorescence and photoelectron excitation and requires no additional energy source. The emission is characterized by an atmospheric temperature of 530 K and an H2 column density of 10(exp 20) cm(exp -2). The dayglow spectrum contains a cascade contribution to the Lyman band emission from high-lying E and F states. Its relative weakness at short wavelengths is due to both self-absorption by H2 and absorption by CH4. Strong wavelength coincidences of solar emission lines and absorption lines of H2 and HD produce unique line spectra which can be identified in the dayglow spectrum. The strongest fluorescence is due to absorption of the solar Lyman-beta line at 1025.72 A by the P(1) line of the (6, 0) Lyman band of H2 at 1025.93 A. The fluorescence lines due to absorption of the solar O 6 line at 1031.91 A by vibrationally excited H2 via the Q(3) line of the (1, 1) Werner band at 1031.86 A are identified. The fluorescence lines provide a sensitive measure of the atmospheric temperature. There occurs an exact coincidence of the solar O 6 line at 1031.91 A and the R(0) line of the (6, 0) Lyman band of HD at 1031-91 A, but HD on Jupiter is difficult to detect due to the dominance of the H2 emission where the HD emission is particularly strong. Higher spectral resolution and higher sensitivity may make possible such a detection. The high resolution (0.3 A) spectra of H2 and HD are presented to stimulate search for the HD on Jupiter with the Hubble Space Telescope.

Liu, Weihong↗
DOE OSTI2022

Electronic Configuration Assignments for UO from Electric Dipole Moment Measurements

Diatomic UO has more than 48 bound states within 10000 cm -1 of the ground state. This electronic state congestion has been attributed to interleaved states from the electronic configurations U 2+ ($5f^37s$)O 2- and U 2+ ($5f^27s^2$)O 2- , respectively. Ligand field theory predicts that each electronic configuration will exhibit states with distinguishable, characteristic vibrational and rotational constants. However, vibronic state mixing modifies the observed vibration–rotation constants, leading to uncertainty in the configurational assignments. The permanent electric dipole moment ($μ_e$) of an electronic state should also manifest a value that is characteristic of the parent electronic configuration. $μ_e$ and other electrostatic and magnetostatic properties should be less influenced by the vibronic state mixing, providing more robust indicators for configurational assignments. In the present study, we have measured the $μ_e$ values for four electronic states of UO. Here, the results clearly demonstrate that the ground state (X(1)4) and the first electronically excited state ((2)4) are derived from the U 2+ ($5f^37s$)O 2– and U 2+ ($5f^27s^2$)O 2– configurations, respectively.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution

Mechanistic insights into photodissociation dynamics of transition metal carbonyls, like Fe(CO) 5 , are fundamental for understanding active catalytic intermediates. Although extensively studied, the structural dynamics of these systems remain elusive. Using ultrafast X-ray scattering, we uncover the photochemistry of Fe(CO) 5 in real space and time, observing synchronous oscillations in atomic pair distances, followed by a prompt rotating CO release preferentially in the axial direction. This behavior aligns with simulations, reflecting the interplay between the axial Fe-C distances’ potential energy landscape and non-adiabatic transitions between metal-to-ligand charge-transfer states. Additionally, we characterize a secondary delayed CO release associated with a reduction of Fe-C steady state distances and structural dynamics of the formed Fe(CO) 4 . Our results quantify energy redistribution across vibration, rotation, and translation degrees of freedom, offering a microscopic view of complex structural dynamics, enhancing our grasp on Fe(CO) 5 photodissociation, and advancing our understanding of transition metal catalytic systems.

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

Elucidating the Atomic Structures of the Gel Layer Formed during Aluminoborosilicate Glass Dissolution: An Integrated Experimental and Simulation Study

The altered glasses produced during aqueous dissolution of silicate and borosilicate glasses are among the most complex structures to understand at the atomic level due to their amorphous nature, random porosity and various levels of hydration. In this study, we gained insights of the complex atomic structures of altered aluminoborosilicate glasses by combining a range of experimental and computational approaches. The altered glasses were prepared by dissolution of three glasses with varying level of alumina in acid for 7 days. A comprehensive set of experimental [elemental analysis, high-energy X-ray diffraction, 29 Si and 27 Al solid-state nuclear magnetic resonance (NMR), and O 1s X-ray photoelectron spectroscopy (XPS)] and modeling (molecular dynamics (MD) simulations using non-reactive and reactive force fields) were used to study the atomic structures of these altered glasses. Elemental analysis showed that most of the B in the pristine glasses was leached into the solution and was not contained in the altered glass. The 29 Si and 27 Al solid-state NMR spectra revealed that the altered glasses have more polymerized silicate network as compared to those in the pristine glasses due to the reformation of linkages among Si and Al oxygen polyhedral in the altered glasses. The bridging and non-bridging (or hydroxyl O) atoms in the altered glasses were also quantified from their O 1s XPS spectra. Atomic structure models of the altered glasses were constructed by using MD simulations using the reactive force field based on the compositional information obtained from experiments. Various pore structures were generated using the charge-scaling (CS) method by using different initial densities and CS temperatures; the best CS parameters of each alternated glass were then determined by comparing with the experimental structure factors obtained from high energy X-ray diffraction. Pore and the atomic structures and vibrational properties around these pore surfaces were analyzed. Furthermore, these results from this comprehensive study thus provides a realistic insight into the pore morphology, atomic structure, and vibrational properties of altered glasses.

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

In situ recording of Mars soundscape

Abstract Before the Perseverance rover landing, the acoustic environment of Mars was unknown. Models predicted that: (1) atmospheric turbulence changes at centimetre scales or smaller at the point where molecular viscosity converts kinetic energy into heat 1 , (2) the speed of sound varies at the surface with frequency 2,3 and (3) high-frequency waves are strongly attenuated with distance in CO 2 (refs. 2–4 ). However, theoretical models were uncertain because of a lack of experimental data at low pressure and the difficulty to characterize turbulence or attenuation in a closed environment. Here, using Perseverance microphone recordings, we present the first characterization of the acoustic environment on Mars and pressure fluctuations in the audible range and beyond, from 20 Hz to 50 kHz. We find that atmospheric sounds extend measurements of pressure variations down to 1,000 times smaller scales than ever observed before, showing a dissipative regime extending over five orders of magnitude in energy. Using point sources of sound (Ingenuity rotorcraft, laser-induced sparks), we highlight two distinct values for the speed of sound that are about 10 m s −1 apart below and above 240 Hz, a unique characteristic of low-pressure CO 2 -dominated atmosphere. We also provide the acoustic attenuation with distance above 2 kHz, allowing us to explain the large contribution of the CO 2 vibrational relaxation in the audible range. These results establish a ground truth for the modelling of acoustic processes, which is critical for studies in atmospheres such as those of Mars and Venus.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Characterization of plasma catalytic decomposition of methane: role of atomic O and reaction mechanism

In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted methane oxidation over a Ni-SiO 2 /Al 2 O 3 catalyst. We evaluated possible reaction mechanisms by analyzing the correlation of gas phase, surface and plasma-produced species. Plasma feed gas compositions, plasma powers, and catalyst temperatures were varied to expand the experimental parameters. Real-time Fourier-transform infrared spectroscopy was applied to quantify gas phase species from the reactions. The reactive incident fluxes generated by plasma were measured by molecular beam mass spectroscopy using an identical APPJ operating at the same conditions. A strong correlation of the quantified fluxes of plasma-produced atomic oxygen with that of CH 4 consumption, and CO and CO 2 formation implies that O atoms play an essential role in CH 4 oxidation for the investigated conditions. With the integration of APPJ, the apparent activation energy was lowered and a synergistic effect of 30% was observed. We also performed in-situ diffuse reflectance infrared Fourier-transform spectroscopy to analyze the catalyst surface. The surface analysis showed that surface CO abundance mirrored the surface coverage of CH n at 25 °C. This suggests that CH n adsorbed on the catalyst surface as an intermediate species that was subsequently transformed into surface CO. We observed very little surface CH n absorbance at 500 °C, while a ten-fold increase of surface CO and stronger CO 2 absorption were seen. This indicates that for a nickel catalyst at 500 °C, the dissociation of CH 4 to CHn may be the rate-determining step in the plasma-assisted CH 4 oxidation for our conditions. We also found the CO vibrational frequency changes from 2143 cm –1 for gas phase CO to 2196 cm –1 for CO on a 25 °C catalyst surface, whereas the frequency of CO on a 500 °C catalyst was 2188 cm –1 . Here, the change in CO vibrational frequency may be related to the oxidation of the catalyst.

methane oxidation↗
DOE OSTI2022

Synthetic Control of Exciton Dynamics in Bioinspired Cofacial Porphyrin Dimers

Understanding how the complex interplay among excitonic interactions, vibronic couplings, and reorganization energy determines coherence-enabled transport mechanisms is a grand challenge with both foundational implications and potential payoffs for energy science. We use a combined experimental and theoretical approach to show how a modest change in structure may be used to modify the exciton delocalization, tune electronic and vibrational coherences, and alter the mechanism of exciton transfer in covalently linked cofacial Zn-porphyrin dimers (meso-beta linked AB m-β and meso-meso linked AA m-m ). While both AB m-β and AA m-m feature zinc porphyrins linked by a 1,2-phenylene bridge, differences in the interporphyrin connectivity set the lateral shift between macrocycles, reducing electronic coupling in AB m-β and resulting in a localized exciton. Pump-probe experiments show that the exciton dynamics is faster by almost an order of magnitude in the strongly coupled AA m-m dimer, and two-dimensional electronic spectroscopy (2DES) identifies a vibronic coherence that is absent in AB m-β . Theoretical studies indicate how the interchromophore interactions in these structures, and their system-bath couplings, influence excitonic delocalization and vibronic coherence-enabled rapid exciton transport dynamics. Real-time path integral calculations reproduce the exciton transfer kinetics observed experimentally and find that the linking-modulated exciton delocalization strongly enhances the contribution of vibronic coherences to the exciton transfer mechanism, and that this coherence accelerates the exciton transfer dynamics. These benchmark molecular design, 2DES, and theoretical studies provide a foundation for directed explorations of nonclassical effects on exciton dynamics in multiporphyrin assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Expression of Novel Gene Products Upregulated by Disuse is Normalized by an Osteogenic Mechanical Stimulus: Evidence for the Molecular Basis of a Low Level Biomechanical Countermeasure for Osteoporosis?

The National Research Council's report entitled: A Strategy for Space Biology and Medical Science, highlighted several areas of fundamental scientific investigation which must be addressed to make long-term space exploration not only feasible, but safe. This "Goldberg Strategy," as well as several subsequent reports published by the NRC's Space Studies Board (e.g., Assessment of Programs in Space Biology and Medicine, Smith et. al., 1991), suggests that the principal hurdle to man's extended presence in space is the osteopenia which parallels reduced gravity. Ironically, the most significant risk to the skeleton may only be realized on return to normal gravitational fields, and full recovery of bone mass may never occur. Effective counter-measures to this microgravity induced bone loss are thus essential. Considering the similarities of space and aging induced osteopenia, an indisputable benefit of such a prophylaxis would be its potential as a treatment for the bone loss which plagues over 25 million people in the U.S. The osteogenic potential of mechanical strain is strongly frequency dependent, with sensitivity increasing up through at least 60 Hz (cycles per second). One hundred seconds per day of a 1 Hz cyclic loading will inhibit disuse osteopenia only if sufficient in magnitude to engender 1000 microstrain (mu(epsilon)) in the tissue. When loading is applied at 30 Hz, however, mechanical strains on the order of 5O mu(epsilon) (approx. 1% of the peak strains which occur in bone during vigorous functional activity), can stimulate bone formation in a duration dependent manner. In longer term animal studies, strains of less than 10 mu(epsilon), induced non-invasively via a whole body vibration, will stimulate bone formation on the surfaces of trabeculae, increase bone density, and improve strength. Finally, preliminary results from a double blind prospective clinical trial shows promise in inhibiting the bone loss which parallels the menopause. Based on these observations, we propose that these high frequency, low magnitude, mechanical strains effectively serve as a "surrogate" for musculoskeletal ground reaction forces, and thus represent an ideal countermeasure to the osteopenia which parallels microgravity conditions. The specific goal of this NASA funded work is to identify genes in bone upregulated by disuse, and to determine the efficacy of an osteogenic mechanical stimulus to downregulate their expression.

Rubin, C.↗
NASA NTRS2018

New O+CO2 Scattering Cross Sections and Their Impact on Photochemical Atmospheric Escape of Oxygen from Mars

Dissociative recombination of O2+ and CO2+ molecular ions in the upper atmosphere of Mars is a major source of suprathermal (hot) oxygen atoms. A significant fraction of hot O atoms are sufficiently fast to overcome Mars' gravitational potential and escape to space. This mechanism is known as photochemical escape (PE) and found to be one of the major escape mechanisms presently active on Mars. The Mars Atmosphere and Volatile Evolution Mission (MAVEN) can constrain the PE rate from measurements of electron temperature and density and ion temperature and density. Escape probabilities of hot O can then be constructed from in-situ neutral densities and escaping O flux loss due to collisions with atmospheric background gases. Due to CO2 abundance in the upper atmosphere, O+CO2 scattering is the most important sink of the escaping hot O flux that strongly affects estimates of total atomic oxygen escape rate obtained from MAVEN data, as outlined above. New O+CO2 elastic and inelastic cross sections were constructed from first principles for collision energies from 0.01-5 eV. O(3P)+CO2 collisions were described using new 4D electronic potential energy surfaces (PESs) for restricted geometries. Three lowest triplet states of CO2 were considered for symmetric, bending, and asymmetric vibrational modes. The cross sections were determined from close-coupling calculations performed on individual surfaces using vibrating rotor approximations for CO2 molecule. Differential and momentum transfer cross sections, of use in energy transfer atmospheric models, were also constructed. The obtained cross sections are in excellent agreement with published results. Our new elastic cross sections are significantly smaller than assumed in earlier atmospheric escape models, resulting in larger photochemical escape rate of O from Mars, as estimated from a 1D escape model. Our results agree well with estimated hot O flux (about 9 x 10(sup 25) s(sup -1)) derived from altitude profiles of 130.4 nm O emission measured up to ~4,000 km by the Imaging Ultraviolet Spectrograph on MAVEN orbiter.

Atmospheric↗
DOE OSTI2021

Threshold Ionization Spectroscopy and Theoretical Calculations of LnO (Ln = La and Ce)

Mass-analyzed threshold ionization (MATI) spectroscopy was used to measure the vibronic spectra of LnO (Ln = La and Ce). Single-reference coupled cluster and relativistic multireference configuration calculations were carried out to compare with the measured vibronic energies. The spectrum of LaO displays a single vibronic band system, while that of CeO shows multiple ones. The ionization energies of LaO and CeO are measured as 5.2446 (6) and 5.3332(6) eV, respectively, which are a hundredfold improvement over the literature values. The vibrational energies of the neutral molecule and corresponding ion reveal the charge effect on the metal-oxygen bond of both species. The single band system in the spectrum of LaO arises from the transition of the ground state of the neutral molecule with the La(6s 1 )O(2p 6 ) valence configuration to the ground state of the singly charged ion with the La(6s o )O(2p 6 ) configuration. Here, the multiple band systems in the spectrum of CeO are attributed to the spin-orbit coupling for the Ce(4f 1 6s 1 )O(2p 6 ) configuration of the neutral molecule and an excited state for the Ce(4f 1 )O(2p 6 ) configuration of the ion.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Ultrafast conformational dynamics of Rydberg-excited N -methyl piperidine

We have observed the ultrafast conformational dynamics of electronically excited N-methyl piperidine (NMP) using time-resolved Rydberg fingerprint spectroscopy. Optical excitation at various wavelengths ranging from 212 nm to 229 nm leads to the 3s or 3p Rydberg states and induces coherent oscillatory motions with periods of about 700 fs. Furthermore, these coherent motions survive the internal conversion from 3p to 3s but then dephase on a time scale of a few oscillations. Intramolecular vibrational energy redistribution on a picosecond time scale leads to an equilibrium between two conformeric structures that are separated in binding energy by 0.09 eV. Model calculations using the DFT-SIC method are in excellent agreement with the experiments and identify the conformers as the chair and twist structures of NMP. The analysis of the equilibrium parameters at long time delays as a function of excitation wavelength allows for the extraction of thermodynamic parameters for the conformeric transformation. We derive an enthalpy of the chair to twist reaction in the 3s excited state of 62 meV with an entropy of 19.70 J mol –1 K –1 . An activation energy of 276 meV is also obtained with a kinetic model.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1998

Thermal Water Vapor Emission from Shocked Regions in Orion

Using the Long Wavelength Spectrometer on board the Infrared Space Observatory, we have observed thermal water vapor emission from a roughly circular field of view approximately 75" in diameter centered on the Orion BN-KL region. The Fabry-Perot line strengths, line widths, and spectral line shifts observed in eight transitions between 71 and 125 micron show good agreement with models of thermal emission arising from a molecular cloud subjected to a magnetohydrodynamic C-type shock. Both the breadth and the relative strengths of the observed lines argue for emission from a shock rather than from warm quiescent gas in the Orion core. Although one of the eight transitions appears anomalously strong and may be subject to the effects of radiative pumping, the other seven indicate an H2O/H2 abundance ratio on the order of 5 x 10(exp -4) and a corresponding gas-phase oxygen-to-hydrogen abundance ratio on the order of 4 x 10(exp -4). Given current estimates of the interstellar, gas-phase, oxygen and carbon abundances in the solar vicinity, this value is consistent with theoretical shock models that predict the conversion into water of all the gas-phase oxygen that is not bound as CO. The overall cooling provided by rotational transitions of H2O in this region appears to be comparable to the cooling through rotational lines of CO but is an order of magnitude lower than cooling through H2 emission. However, the model that best fits our observations shows cooling by H2O and CO dominant in that portion of the postshock region where temperatures are below approximately 800 K and neither vibrational nor rotational radiative cooling by H2 is appreciable.

Harwitt, Martin↗
DOE OSTI2020

Photoabsorption, photoionization, and Auger processes at the carbon K edge in C H 3 I

The dynamics of photoabsorption, photoionization, and the associated Auger decay have been investigated at the carbon K edge in methyl iodide (CH 3 I) using linearly polarized synchrotron radiation. Ion yield measurements were used to investigate transitions in the pre-edge region due to excitations into either unoccupied valence or Rydberg states. The assignment of these transitions was achieved through comparison with theoretical x-ray absorption spectra calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation. Several of the Rydberg states belonging to series converging onto the C1s ionization limit exhibit significant vibrational structure that is also interpreted using theoretical calculations. The C1s in CH 3 I photoelectron spectrum was measured, and the observed vibrational structure was assigned with the aid of theoretical predictions. Polarization dependent, resonantly excited, valence shell photoelectron spectra were recorded at photon energies coinciding with the C1s → σ*, C1s → 6sa1 and C1s → 6pe transitions in CH 3 I , thereby allowing photoelectron angular distributions to be determined. The nonresonantly excited C(KVV) Auger electron spectrum was measured and some of the features observed at high kinetic energies were attributed to transitions into valence orbitals possessing significant iodine character. The contributions of participator and spectator Auger decay to the resonantly excited photoelectron spectra have been assessed. The influence of participator decay appears minor whereas spectator decay results in the enhanced population of satellite states.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2001

Organic Signature of Dust from the Interstellar Medium (ISM)

Dust in the ISM carries an "organic" signature in form of a distinct group of C-H stretching bands, both in emission and absorption, around 3.4 micrometers. These bands agree with the symmetrical and asymmetrical C-H stretching vibrations of aliphatic -CH2- entities and are thought to be associated with organic molecules on the surface of dust grains. We show that this interpretation is inconsistent with laboratory experiments. Synthetic MgO and natural olivine single crystals, grown from a CO/CO2/H2O-saturated melt, exhibit the same C-H stretching bands but those bands are clearly associated with C-H entities inside the dense mineral matrix. The multitude of C-H stretching bands suggests that the C-H bonds arise from polyatomic C(sub n) entities. We heated the MgO and olivine crystals to temperatures between 550-1000 K to pyrolyze the C-H bonds and to cause the C-H stretching bands to disappear. Upon annealing at moderate temperatures between 300-390 K the C-H stretching bands reappear within a few days to weeks. The C-H stretching band intensity increases linearly with the square root of time. Thus, while the pyrolysis broke the C-H bonds and caused the H to disperse in the mineral matrix, the H atoms (or H2 molecules) are sufficiently mobile to return during annealing and reestablish the C-H bonds. Dust grains that condense in a gas-laden environment (outflow of late-stage stars or in dense molecular clouds) probably incorporate the same type of Cn-H entities. Imbedded in and in part bonded to the surrounding mineral matrix, the Cn-H entities display C-H stretching bands in the 3.4 micrometer region, but their lower frequency librational modes are so strongly coupled to the lattice modes that they broaden excessively and thus become unobservable.

Freund, Friedemann↗
NASA NTRS2018

Quantitative validation of Ames IR intensity and new line lists for (32/33/34)S(16)O2, (32)S(18)O2 and (16)O(32)S(18)O

The quality of Ames-296K SO2 Infrared (IR) line list intensities is first validated by quantitative exploration of several dipole moment surfaces (DMSs) and partition sum convergence. The DMSs are computed with several of Dunning’s correlation-consistent basis sets and their vibrational dependence are compared to the empirical model derived from Stark effect experiments reported by D. Patel, D. Margolese, and T.R. Dykea [J.Chem.Phys. 70, 2740 (1979)]. The effective dipole deviations from the DMS adopted in the Ames IR lists is 0.2-0.4% for vibrational states up to 3v3. The vibrational dependence of the dipole moment is also in good agreement, except for nv1. Partition sum convergence at 296K is confirmed by new calculations with rotational quantum number J up to 150 and upper state E’ up to 8000 cm-1. The isotopologue consistency of the Ames IR line lists is superior relative to the regular Effective Hamiltonian (EH) models and Effective Dipole Moment (EDM) models. The v1+v2 and v2+v3 intensity consistency check reveals the recently reported experimental intensities need significant improvement or re-analysis. After the accuracy, convergence, and isotopologue consistency have been confirmed, the theoretical Ames-296K intensities are combined with the experimental line positions or EH models that experimental spectroscopists published after 2009. Three high-resolution IR line sets are reported for the (32/33/34)S(16)O2, (32)S(18)O2 and (16)O(32)S(18)O isotopologues: (1) the “New Lines Sets” include experimentally measured line positions; (2) the “Expanded Line Sets” include possible transitions among new rovibrational levels assigned in experiments and ground state (GS) levels predicted by reliable EH models; (3) the “Ames + MARVEL Sets” include possible transitions among all those levels reported in a recent MARVEL analysis. [Tóbiás et al, JQSRT 208, 152 (2018)]. Compared to the limited data in High-resolution TRANsmission molecular absorption database (HITRAN), these line sets have significantly improved the data coverage up to 4000 cm-1. Some missing bands can be traced to the unpublished experimental data. The isotopologue consistency of these line sets will help identify the uncertainties and defects in the experimental EH and EDM models. These line sets are good candidates for the next HITRAN update, if line shape parameters are available. The line sets can be downloaded from supplementary files or from the Ames Molecular Spectroscopic Database at http://huang.seti.org.

Xinchuan Huang↗
DOE OSTI2024

Hydrogenation of calcite and change in chemical bonding at high pressure: Diamond formation above 100GPa

Synchrotron X-ray diffraction (XRD) and Raman spectroscopy in laser heated diamond anvil cells and first principles molecular dynamics (FPMD) calculations have been used to investigate the reactivity of calcite and molecular hydrogen (H 2 ) at high pressures up to 120 GPa. We find that hydrogen reacts with calcite starting below 0.5 GPa at room temperature forming chemical bonds with carbon and oxygen. This results in the unit cell volume expansion; the hydrogenation level is much higher for powdered samples. Single-crystal XRD measurements at 8–24 GPa reveal the presence of previously reported III, IIIb, and VI calcite phases; some crystallites show up to 4% expansion, which is consistent with the incorporation of ≤ 1 hydrogen atom per formula unit. At 40–102 GPa XRD patterns of hydrogenated calcite demonstrate broadened features consistent with the calcite VI structure with incorporated hydrogen atoms. Above 80 GPa, the C–O stretching mode of calcite splits suggesting a change in the coordination of C–O bonds. Laser heating at 110 GPa results in the formation of C–C bonds manifested in the crystallization of diamond recorded by in situ XRD at 300 K and 110 GPa and by Raman spectroscopy on recovered samples commenced with C 13 calcite. We explored several theoretical models, which show that incorporation of atomic hydrogen results in local distortions of CO 3 groups, formation of corner-shared C–O polyhedra, and chemical bonding of H to C and O, which leads to the lattice expansion and vibrational features consistent with the experiments. In conclusion, the experimental and theoretical results support recent reports on tetrahedral C coordination in high-pressure carbonate glasses and suggest a possible source of the origin of ultradeep diamonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗