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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Oxygen-atom transfer photochemistry of a molecular copper bromate complex

Here, we report the synthesis and oxygen-atom transfer (OAT) photochemistry of [Cu(tpa)BrO 3 ]ClO 4 . In situ spectroscopy and in crystallo experiments indicate OAT proceeds from a Cu–O fragment generated by sequential Cu–O bond cleavage and OAT from BrO x to [Cu(tpa)] + . Furthermore, these results highlight synthetic opportunities in M–O photochemistry and demonstrate the utility of in crystallo experiments to evaluating photochemical reaction mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2016

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as delta36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher delta36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower delta36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-delta36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where delta36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in delta36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a +/-10 percent range since 1978.

oxygen↗
DOE OSTI2025

In Crystallo Photochemistry: Reimagining Synthetic Tractability with Transparent Single-Crystalline Flasks

Expanding the boundaries of synthetic tractability of what molecules can be synthesized and isolated is an eternal challenge for synthetic chemists. The development of new synthetic methods and strategies enables the properties and potential functions of novel molecular targets to be experimentally evaluated. In the context of catalysis, predictable synthetic strategies are often available to access kinetically persistent intermediates such as catalyst resting states. In contrast, synthesis and characterization of the reactive intermediates are often not possible due to the fleeting lifetimes of these species. In crystallo photochemistry combines single-crystal matrix isolation with cryogenic photochemistry to enable reactive intermediates to be synthesized under conditions in which they are persistent and can be (crystallographically) characterized. This Outlook highlights key achievements of in crystallo photochemistry as well as discusses opportunities and challenges that confront realization of the potential of in crystallo synthesis to redefine the boundaries of synthetic tractability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nonadiabatic Dynamics Simulation of the Wavelength-Dependent Photochemistry of Azobenzene Excited to the nπ* and ππ* Excited States

Azobenzene is one of the most ubiquitous photoswitches in photochemistry and a prototypical model for photoisomerizing systems. Despite this, its wavelength-dependent photochemistry has puzzled researchers for decades. Upon excitation to the higher energy ππ* excited state instead of the dipole-forbidden nπ* state, the quantum yield of isomerization from trans- to cis-azobenzene is halved. The difficulties associated with unambiguously resolving this effect both experimentally and theoretically have contributed to lasting controversies regarding the photochemistry of azobenzene. Here, we systematically characterize the dynamic photoreaction pathways of azobenzene by performing first-principles simulations of the nonadiabatic dynamics following excitation to both the ππ* and the nπ* states. In this work, we demonstrate that ground-state recovery is mediated by two distinct S1 decay pathways: a reactive twisting pathway and an unreactive planar pathway. Increased preference for the unreactive pathway upon ππ* excitation largely accounts for the wavelength-dependent behavior observed in azobenzene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ultrafast photochemistry of gas-phase transition metal carbonyls

Organometallic photochemistry lies at the heart of photochemical energy conversions in applications such as photocatalysis, photovoltaic cells, and luminescent materials. Thus, understanding how metal and ligand interactions in organometallic complexes modify electronic excited-state properties and reactivity has been the subject of intense studies for decades. Transition metal carbonyls [M n (CO) m ] have long served as prototypical organometallic complexes for understanding metal–ligand bonding and photochemistry and have been studied extensively in solution, matrices, and the gas phase on time scales ranging from femtoseconds to microseconds and longer. This review chronicles the past two and a half decades of efforts in understanding the ultrafast (sub-nanosecond) dynamics of transition metal carbonyls in the gas phase, where complicating solvent influences are absent and multiple experimental probes and high-level electronic structure theory can come together to yield rich information on the intricate interplay of electronic and structural dynamics. This review first lays the groundwork by briefly describing the electronic structure of transition metal carbonyls and introducing the various ultrafast techniques that have been applied to study their unimolecular dynamics. We then provide a detailed historical account on the ultrafast photochemistry of iron pentacarbonyl, nickel tetracarbonyl, and transition metal hexacarbonyls and decacarbonyls, putting the more recent ultrafast studies in the context of prior investigations. In conclusion, we end this review with an outlook on open questions and future possibilities.

Core level spectroscopy↗
NASA NTRS2020

UV/Vis+ Photochemistry Database: Structure, Content and Applications

The “science-softCon UV/Vis+ Photochemistry Database” (www.photochemistry.org) is a large and comprehensive collection of EUV-VUV-UV–Vis-NIR spectral data and other photochemical information assembled from published peer-reviewed papers. The database contains photochemical data including absorption, fluorescence, photoelectron, and circular and linear dichroism spectra, as well as quantum yields and photolysis related data that are critically needed in many scientific disciplines. This manuscript gives an outline regarding the structure and content of the “science-softCon UV/Vis+ Photochemistry Database”. The accurate and reliable molecular level information provided in this database is fundamental in nature and helps in proceeding further to understand photon, electron and ion induced chemistry of molecules of interest not only in spectroscopy, astrochemistry, astrophysics, Earth and planetary sciences, environmental chemistry, plasma physics, combustion chemistry but also in applied fields such as medical diagnostics, pharmaceutical sciences, biochemistry, agriculture, and catalysis. In order to illustrate this, we illustrate the use of the UV/Vis+ Photochemistry Database in four different fields of scientific endeavor.

Photochemistry↗
DOE OSTI2024

Performance of chatbots in queries concerning fundamental concepts in photochemistry

Abstract The advent of chatbots raises the possibility of a paradigm shift across society including the most technical of fields with regard to access to information, generation of knowledge, and dissemination of education and training. Photochemistry is a scientific endeavor with roots in chemistry and physics and branches that encompass diverse disciplines ranging from astronomy to zoology. Here, five chatbots have each been challenged with 13 photochemically relevant queries. The chatbots included ChatGPT 3.5, ChatGPT 4.0, Copilot, Gemini Advanced, and Meta AI. The queries encompassed fundamental concepts (e.g., “Why is the fluorescence spectrum typically the mirror image of the absorption spectrum?”), practical matters (e.g., “What is the inner filter effect and how to avoid it?”), philosophical matters (“Please create the most important photochemistry questions.”), and specific molecular features (e.g., “Why are azo dyes non‐fluorescent?”). The chatbots were moderately effective in answering queries concerning fundamental concepts in photochemistry but were glaringly deficient in specialized queries for dyes and fluorophores. In some instances, a correct response was embedded in verbose scientific nonsense whereas in others the entire response, while grammatically correct, was utterly meaningless. The unreliable accuracy makes present chatbots poorly suited for unaided educational purposes and highlights the importance of domain experts.

Taniguchi, Masahiko↗
NASA NTRS1980

Hydrocarbon photochemistry and Lyman alpha albedo of Jupiter

A combined study of hydrocarbon and atomic hydrogen photochemistry is made to calculate self-consistently the L alpha albedo of Jupiter. It is shown that the L alpha emissions observed by Voyagers I and II can be explained by resonance scattering of sunlight. Precipitation of energetic particles from the magnetosphere can provide the large required source of atomic hydrogen, although the contribution of direct particle excitation to the disk-averaged brightness is insignificant. The variability of the L alpha brightness inferred from many observations in recent years is examined. The large difference in the brightness of the He 584 A resonance line observed by Pioneer and Voyager is briefly discussed. Driving the photochemistry by solar ultraviolet radiation alone yields a maximum mixing ratio of C2H6 + C2H2 at 0.01 atm of about 4 x 10 to the -6th. The possibility of additional CH4 dissociation from precipitation of magnetospheric particles is discussed. The photochemistry of C2H2 and C2H3 is sufficiently uncertain not to permit accurate calculations of their densities and the ratio C2H6/C2H2.

Yung, Y. L.↗
NASA NTRS1984

Phosphine photochemistry in the atmosphere of Saturn

The photochemistry of PH3 in the atmosphere of Saturn is studied, including the effects of coupling with the photochemistries of NH3 and hydrocarbons. The vertical concentration of PH3 is found to be extremely sensitive to the eddy diffusion coefficient (K) profile used. If K is roughly 10,000 sq cm/sec in the upper troposphere, PH3 should be depleted there with a scale height of about 3.5 km. An upper limit of 100,000 sq cm/sec is estimated for K. If the gas phase concentration of P2H4 can be neglected, production of molecular phophorus is very unlikely unless the spin-forbidden recombination reaction PH+H2+M - PH3+M occurs with an exceptionally low rate. Coupling of PH3 and hydrocarbon photochemistries is very important. Possible observable amounts of the organophosphorus molecules CH3PH2 and HCP are tentatively predicted.

Kaye, J. A.↗
NASA NTRS2003

Spectra and Photochemistry of Relevance to Icy Outer Solar System Objects

The Astrochemistry Lab at NASA Ames (www.astrochem.org) has an interest in the organic photochemistry of extraterrestrial ices, having traditionally performed experiments under interstellar conditions. We have recently embarked on projects for PG\&G to measure spectra and elucidate the photochemistry of ices relevant to outer Solar System objects. 1) We will report on the determination of real and imaginary indicies of refraction of H2O and N2 dominated ices containing simple, common, extraterrestrial molecules such as NH3, HCN, formaldehyde, \& methanol. 2) We will compare and contrast the photochemistry of H2O ices containing organic molecules at 100 K with previously reported work at 15 K.

Bernstein, M. P.↗
NASA NTRS2007

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively small boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Grannas, A. M.↗
DOE OSTI2023

Photochemistry sample sticks for inelastic neutron scattering

Every material experiences atomic and molecular motions that are generally termed vibrations in gases and liquids or phonons in solid state materials. Optical spectroscopy techniques, such as Raman, infrared absorption spectroscopy, or inelastic neutron scattering (INS), can be used to measure the vibrational/phonon spectrum of ground state materials properties. A variety of optical pump probe spectroscopies enable the measurement of excited states or elucidate photochemical reaction pathways and kinetics. So far, it has not been possible to study photoactive materials or processes in situ using INS due to the mismatch between neutron and photon penetration depths, differences between the flux density of photons and neutrons, cryogenic temperatures for INS measurements, vacuum conditions, and a lack of optical access to the sample space. These experimental hurdles have resulted in very limited photochemistry studies using INS. Here we report on the design of two different photochemistry sample sticks that overcome these experimental hurdles to enable in situ photochemical studies using INS, specifically at the VISION instrument at Oak Ridge National Laboratory. We demonstrate the use of these new measurement capabilities through (1) the in situ photodimerization of anthracene and (2) the in situ photopolymerization of a 405 nm photoresin using 405 nm excitation as simple test cases. Furthermore, these new measurement apparatus broaden the science enabled by INS to include photoactive materials, optically excited states, and photoinitiated reactions.

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

Annihilating Actinic Photochemistry of the Pyruvate Anion by One and Two Water Molecules

Photochemical behaviors of pyruvic acid in multiple phases have been extensively studied, while those of its conjugate base, the pyruvate anion (CH 3 COCOO – , PA – ) are less understood and remain contradictory in gaseous versus aqueous phases. Here in this article, we report a joint experimental and theoretical study combining cryogenic, wavelength-resolved negative ion photoelectron spectroscopy (NIPES) and high-level quantum chemical computations to investigate PA – actinic photochemistry and its dependence on microsolvation in the gas phase. PA – ·nH 2 O (n = 0–5) clusters were generated and characterized, with their low-lying isomers identified. NIPES conducted at multiple wavelengths across the PA – actinic regime revealed the PA – photochemistry extremely sensitive to its hydration extent. While bare PA – anions exhibit active photoinduced dissociations that generate the acetyl (CH 3 CO – ), methide (CH 3 – ) anions, their corresponding radicals, and slow electrons, one single attached water molecule results in significant suppression with a subsequent second water being able to completely block all dissociation pathways, effectively annihilating all PA – photochemical reactivities. Further, the underlying dissociation mechanisms of PA – ·nH 2 O (n = 0–2) clusters are proposed involving nπ* excitation, dehydration, decarboxylation, and further CO loss. Since the photoexcited dihydrate does not have sufficient energy to overcome the full dehydration barrier before PA – could fragmentate, the PA – dissociation pathway is completely blocked, with the energy most likely released via loss of one water and internal electronic and vibrational relaxations. The insight unraveled in this work provides a much-needed critical link to connect the seemingly conflicting PA – actinic chemistry between the gas and condensed phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Wavelength dependent photochemistry of an iron dinitrogen hydride complex via multiple spectroscopies – competing ejection of axial ligands

Nitrogenase (N 2 ase) is a critical enzyme which catalyzes the reaction of N 2 → NH 3 in nature. Studies on the spectroscopy and photochemistry of trans-[Fe II (DMeOPrPE) 2 (N 2 )H][BPh 4 ] (1) and its isotopologues (2–6) provide a possible first step to evaluate the geometries and properties of the real N 2 ase–N 2 structure(s). In this article, we have used FT-IR, FT-Raman, synchrotron-based nuclear resonant vibrational spectroscopy (NRVS) and DFT calculations to examine and assign the normal modes of these complexes. In addition, we have monitored their wavelength dependent photochemistry using mid-IR, near-IR, NRVS, and Mössbauer spectroscopies. Two distinct photolysis pathways are observed with mid-IR at (nominal) 4 K – (1) the cleavage of Fe–N 2 bond in UV or visible light photolyses, which presents a unipolar disappearance of the N 2 peak at 2094 cm −1 and is recombinable; (2) the ejection of trans hydrogen atom with UV irradiation, which has a pair of bipolar peaks with the disappearance of N 2 at 2094 cm −1 and the appearance of a new species at 2056 cm −1 and is non-recombinable. The latter peak is well aligned with the N 2 peak in an Fe I reference complex (7). The combination of mid IR monitored photolysis/recombination and NRVS monitored photolysis form the central evidence for the conclusions in this article. In particular, the Fe II –N 2 and Fe I –H·dissociations are in competition with each other in UV or UV-inclusive photolyses of this dinitrogen hydride complex. In addition, near-IR and Mössbauer also provide consistent evidence about Fe I . This wavelength dependent photochemical work is the first one on a reaction active N 2 ase–N 2 model complex and it also demonstrates the competition ejection between two axial ligands (H· and N 2 ). It offers valuable information for future studies on real N 2 ase–N 2 and its photolysis products.

Dong, Weibing [Liaoning Normal University (China)]↗
NASA NTRS1973

Photochemistry of interstellar molecules

The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.

Stief, L. J.↗
NASA NTRS1977

Tropospheric ozone - Coupling transport and photochemistry

The budget of tropospheric ozone is re-examined in the light of lower observed nitrogen oxide densities and revised reaction rates. To estimate the relative importance of transport and photochemistry, model calculations are presented which determine one-dimensional vertical ozone profiles at midlatitudes for equinoctial conditions. These calculations imply that both photochemistry and transport are important in controlling the abundance of tropospheric ozone. It is estimated that photochemical processes produce about 0.6 times 10 to the eleventh and destroy about 1.4 times 10 to the eleventh tropospheric ozone molecules per sq cm per sec, while mixing processes transport about 1.4 times 10 to the eleventh ozone molecules per sq cm per sec from the stratosphere into the troposphere and ground level fluxes destroy about 0.6 times 10 to the eleventh ozone molecules per sq cm per sec. The sensitivity of our model calculations to transport parameters, key rate coefficients, and nitrogen oxide densities are discussed.

Chameides, W. L.↗
NASA NTRS1978

Feasibility of an orbital simulator of stratospheric photochemistry

It is proposed that a stratospheric photochemistry simulator could be created in sun-synchronous orbit, so that diffusion and photochemistry could be decoupled and uncertainties in photochemical reaction rates could be substantially reduced. The proposed test chamber is described, and it is suggested that the technology of superpressure balloons seems to be the best short-term solution to the construction of the proposed facility. Both unreinforced polyester films and gelatin films are considered as candidate chamber coatings. It is noted that the experiments can be performed early in the space-manufacturing era and that at least three dedicated Shuttle launches will be required to establish the proposed facility.

Matloff, G. L.↗