Search NASA⌕ Search

SEARCH · Search NASA

Results for “isomer”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Differentiating and Quantifying Gas-Phase Conformational Isomers Using Coulomb Explosion Imaging

Conformational isomerism plays a crucial role in defining the physical and chemical properties and biological activity of molecules ranging from simple organic compounds to complex biopolymers. However, it is often a significant challenge to differentiate and separate these isomers experimentally as they can easily interconvert due to their low rotational energy barrier. Here, we use the momentum correlation of fragment ions produced after inner-shell photoionization to distinguish conformational isomers of 1,2-dibromoethane (C 2 H 4 Br 2 ). We demonstrate that the three-body breakup channel, C 2 H 4 + + Br + + Br + , contains signatures of both sequential and concerted breakup, which are decoupled to distinguish the geometries of two conformational isomers and to quantify their relative abundance. The sensitivity of our method to quantify these yields is established by measuring the relative abundance change with sample temperature, which agrees well with calculations. Finally, our study paves the way for using Coulomb explosion imaging to track subtle molecular structural changes.

Photoionization↗
DOE OSTI2025

Time-resolved momentum imaging of UV photodynamics in structural isomers of iodopropane probed by site-selective XUV ionization

The photodynamics of 1- and 2-iodopropane (1 and 2-IP) were studied in a time-resolved scheme incorporating ultraviolet (UV) excitation and extreme ultraviolet (XUV) probing, which initiates photoionization selectively from the I 4d core orbital. UV absorption in the A-band of both isomers leads to prompt C–I bond fission, with significant disposal of internal energy into the propyl radical product. Site-selective ionization enables a range of charge transfer (CT) processes between the nascent highly charged iodine ions and neutral propyl radicals, dependent on the interfragment distance at the instant of ionization. Subtle differences in the dynamics of these CT processes between the two isomers are observed. In 1-IP, the kinetic energies of iodine ions produced by UV photodissociation and subsequent XUV multiple ionization increased notably over the first few hundred femtoseconds, which could be understood in terms of differing gradients along the photodissociation coordinates of the neutral and polycationic states involved in the pump and probe steps, respectively. Led by a recent report of HI elimination in UV photoexcited 2-IP [Todt et al., Phys. Chem. Chem. Phys., 22(46), 27338 (2020)], we also model the most likely signatures of this process in the present experiment, and can identify signal in the 2-IP data (that is absent or significantly weaker in the data from the unbranched 1-IP isomer) that is consistent with such a process occurring on ultrafast timescales.

Allum, Felix [Deutsches Elektronen-Synchrotron (DE↗
DOE OSTI2023

Relativistic and magnetic Breit effects for the reaction Sg + 6CO → Sg(CO)6 and Sg(OC)6: Prediction of the existence and atomization energy of the isomer Sg(OC)6

Our ab initio all-electron fully relativistic Dirac–Fock (DF) and Dirac–Fock–Breit–Gaunt (DFBG) and nonrelativistic (NR) Hartree–Fock (HF) calculations for seaborgium hexacarbonyl Sg(CO)6 predict atomization energies (Ae) of 68.81, 69.28, and 67.69 eV, respectively, at the corresponding optimized octahedral geometry. However, our DF, DFBG, and NR HF calculations for the isomer Sg(OC)6 yield atomization energies of 64.30, 64.77, and 62.62 eV, respectively, at the optimized geometry for this species. The optimized Sg–C and C–O bond distances (in Å) for octahedral Sg(CO)6 using our DF (NR) calculations are 2.15 (2.32) and 1.11 (1.11), respectively. However, the optimized Sg–O and O–C bond distances (in Å) for the isomer octahedral Sg(OC)6 obtained with our DF (NR) calculations are 2.80 (2.73) and 1.10 (1.11), respectively. Our prediction of the greater stability of Sg(CO)6 isomer at both the relativistic (DF and DFBG) and the NR HF levels of theory lends further support to the detection of Sg(CO)6 in the state-of-the-art gas-phase experimental studies of the carbonyl complex of seaborgium reported by Even et al. [Science 345(6203), 1491 (2014)].

Materials Science↗
DOE OSTI2025

Nonadiabatic dynamics of photoexcited thiopyridone isomers: An interplay between El-Sayed’s conditions and energy gap law

We investigated the non-adiabatic dynamics of photoexcited thiopyridone systems across their ortho-, meta-, and para-isomeric forms. The relaxation pathways of the three isomers in both gas phase and solvent environments are mapped using surface hopping dynamics based on time-dependent density functional theory. Our analysis highlights the influence of isomeric structures on photophysical behavior, offering insights into design principles to control photochemical phenomena. The simulations suggest a systematic reduction in the rate of intersystem crossing (ISC) from ortho- to meta- to para-isomer. Comparisons with multiconfigurational wave function methods in the gas phase further demonstrate how electronic structure influences the predicted dynamical pathways. The simulated dynamics demonstrates that the spin–orbit coupling strength alone does not determine the rate of ISC, as both state energetics and underlying electronic and structural features play decisive roles. These aspects explain the much slower ISC in the para-isomer, as well as the non-negligible role of the El-Sayed forbidden pathway in the computed ISC dynamics.

Complete-active space self-consistent field↗
DOE OSTI2024

Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C 6 H 11 O 2 ), building on higher-level reference calculations for the smaller ethane oxidation (C 2 H 5 O 2 ) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Nuclear Isomer Discovery Database Released

Nuclear isomers correspond to excited states in nuclides with finite lifetimes. Here, after the discovery of isotopes–different nuclides of the same element–in 1913 by Frederick Soddy [Citation1], Otto Hahn postulated in 1921 [Citation2] that there are even different metastable states within one isotope. In analogy to chemical isomers, which are the same compounds with distinct structures, nuclear isomers have the same number of protons and neutrons but in different configurations.

Thoennessen, Michael [Michigan State University, E↗
DOE OSTI2026

Contrasting decays of 3-quasiparticle isomers in 173 W: A discerning test of 𝐾 conservation and 𝐾 mixing

Two isomers with K π = 19/2 + at 1876 keV with a half-life of 21(1) ns, and K π = 23/2− at 2159 keV with a half-life of 93(6) ns have been identified in 173 W, the lightest tungsten isotope to exhibit this phenomenon. An unusually high number of 13 branches have been established in the decay of the K π = 23/2 − isomer. This decay is associated with transitions involving significantly higher degrees of K forbiddenness and is in sharp contrast with the usual preferential deexcitation through branches, which are less forbidden, as is evident for the K π = 19/2 + state in 173 W. The inclusion of K-mixing effects, arising from band crossings in the sequences to which decays with larger degrees of K forbiddenness are observed, can qualitatively account for this contrasting behavior. These results provide a striking illustration of the competition between K conservation and K mixing in the decay of such isomers.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Quantum enabled precision measurements of the 229Th nuclear isomer transition (final report)

The existence of the nuclear isomer transition in thorium-229 was first inferred from keV lines in the gamma spectrum of uranium-233 decay more than 40 years ago. Over the years, the value of the transition energy has been refined with indirect measurements using nuclear physics techniques, and the current evidence points to transition energy in the laser-accessible vacuum ultra-violet region of the spectrum. At the start of this project, the two best measurements of the transition energy were 7.8±0.5 eV and 8.28±0.17 eV from high precision gamma ray spectroscopy and kinetic energy of internal conversion electrons, respectively. This project aimed to reduce the uncertainty in the transition energy to 10 meV using direct calorimetric measurements of the decay energy with superconducting nanowire single photon detectors (SNSPDs). Specifically, the method that was pursued was to generate thorium-229 in the excited isomer state by the alpha decay of uranium-233, embed the excited state thorium into an SNSPD, then detect the energy released when the isomer deexcites.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Isomers in Tl 203 and core excitations built on a five-nucleon-hole structure

Isomers with three- and five-nucleon-hole configurations have been established in 203 Tl These include newly identified levels with a three-nucleon-hole structure: I π = (15/2 – ) with T 1/2 = 7.9(5) ns and I π = (35/2 – ) with T 1/2 = 4.0(5) ns. In addition, five-nucleon-hole states have also been established: I π = (39/2 – ) with T 1/2 = 1.9(2) ns and I π = (49/2 + ) with T 1/2 = 3.4(4) ns. The previously determined long-lived decay, T 1/2 = 6.6(3) μs from this work, is associated with isomerism of the I π = (29/2 + ) state. Levels above this long-lived isomer have been identified through a delayed-prompt γ–γ coincidence measurement. Five-nucleon-hole states with excitation energies E x ≈ 7 MeV have been established as well as possible octupole excitations of the 208Pb core built on these levels. Furthermore, the level scheme of 203 Tl is extended up to E x ≈ 11 MeV with the inclusion of 25 new transitions. Empirical and shell-model calculations have been performed to aid in the description of the observed states which are found to be of intrinsic character.

190 ≤ A ≤ 219↗
DOE OSTI2023

Linker Vacancy Engineering of a Robust ftw–type Zr–MOF for Hexane Isomers Separation

Discrimination of physically similar molecules by porous solids represents an important yet challenging task in industrially relevant chemical separations. Precisely controlled pore dimension and/or tailored pore surface functionality are crucial to achieve high-efficiency separation. Metal-organic frameworks (MOFs) are promising candidates for these challenging separations in light of their structural diversity as well as highly adjustable pore dimension/functionality. We report here a microporous, ftw-type Zr-based MOF structure, HIAM-410 (HIAM=Hoffmann Institute of Advanced Materials), built on hexanuclear Zr 6 cluster and pyrene-1,3,6,8-tetracarboxylate (ptc 4– ). Its crystallographic structure has been determined using continuous rotation electron diffraction (cRED) technique combined with Rietveld refinement against powder X-ray diffraction data, aided by low-dose high-resolution transmission electron microscopy (HRTEM) imaging. The compound features exceptional framework stability that is comparable to the prototype MOF UiO-66. Interestingly, the linker vacancies in the pristine MOF structure could be partially restored by post-synthetic linker insertion. Its separation capability of hexane isomers is enhanced substantially upon the linker vacancy engineering. As a result, the restored structure exhibits efficient splitting of monobranched and dibranched hexane isomers at both room temperature and industrially relevant temperature.

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

Unique W-Shape Y6 isomer as effective solid additive for High-Performance PM6:Y6 polymer solar cells

The current top-performing polymer solar cell (PSC) systems are mostly based on PM6:Y6 host blend. To date, numerous materials have been explored as the third component for these systems to form ternary blends or as additives. Vitrification agents are a group of additives proved to be useful in affecting the morphology of organic semiconductors. Here to design a suitable vitrification agent for non-fullerene electron acceptor Y6, an isomer strategy was explored where the thienothiophene wings of the Y6 molecule were inversed to form a W-shaped Y6 isomer of i-Y6. It was found that i-Y6 crystallized poorly with a different packing style than Y6 and could blend well in amorphous phase of Y6. These properties enabled i-Y6 to finely tune the morphology of PM6:Y6 blend at low additive dosages. The power conversion efficiency (PCE) of PM6:Y6 based PSC was raised from 16.827% to 17.433% at a dosage of Y6:i-Y6 ratio of 24:1. This work demonstrated isomerization as a viable strategy for developing solid additives for high performance PSC blends and vitrification agents as effective additives for tuning morphology and improving performances of PSCs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Synthetic aromatic kerosene property prediction improvements with isomer specific characterization via GCxGC and vacuum ultraviolet spectroscopy

This research explores an advanced method of fuel composition determination and builds upon typical hydrocarbon group type analyses performed with two-dimensional gas chromatography (GCxGC). In this study, structural information of individual species within Virent’s Synthetic Aromatic Kerosene (SAK) is identified by vacuum ultraviolet (VUV) spectroscopy. By mass, 71.3% of the components elute within six peaks of the chromatogram, from which 12 unique species are identified through a novel deconvolution method. Overall, the identification of 93.6%m across 26 structural isomers is made by the methods described in this work. With 93.6%m ascribed to specific isomers, the precision of fuel property predictions improves dramatically. For example, the absolute error of the viscosity prediction is reduced by 90% because of this advancement in diagnostic capability, and its 95-percentile confidence interval (precision only) is reduced by 93%. Additionally, the properties of SAK, blended with hydro processed esters fatty acids (HEFA), are demonstrated to have blended properties consistent with conventional jet fuel.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Opportunities for isomer studies for astrophysics at FRIB

The role of nuclear isomers in astrophysical nucleosynthesis is gaining increased attention, as reactions on ground and isomeric states are both potentially important for determining the reaction rates and flow within the reaction network. A particular case is the odd-odd N=Z nuclides in the sd -shell, which play an important role in breakout from the CNO cycle in nova nucleosynthesis, affecting reaction flow, the nucleosynthesis end-point, and final abundances, impacting potential astronomical observables. Because many of these nuclides have low-lying isomers, it is important to constrain reactions on both ground and isomeric states. Developments in radioactive-beam facilities are opening such opportunities, via direct and indirect techniques. The first measurement using a new technique for manipulating ground/isomer content in reaccelerated beams without affecting ion optics, has been employed to study 38 K, which will be applicable to measurements on 34 Cl and others at the nascent Facility for Rare Isotope Beams.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Reply to “Comment on ‘Nomenclature, Chemical Abstracts Service numbers, isomer enumeration, ring strain, and stereochemistry: What does any of this have to do with an international chemical disarmament and nonproliferation treaty?’”

A letter to the Journal of Chemical Education provided comments and accurate enumerations of isomers for sets of organic compounds discussed in the paper “Nomenclature, Chemical Abstracts Service numbers, isomer enumeration, ring strain, and stereochemistry: What does any of this have to do with an international chemical disarmament and nonproliferation treaty?”. This is a reply to that letter to address the comments and propose updates to the original paper in order to incorporate the accurate enumeration values.

Alkanes/Cycloalkanes, Chemical Weapons Convention ↗
DOE OSTI2024

IsoForma: An R Package for Quantifying and Visualizing Positional Isomers in Top-Down LC-MS/MS Data

Proteoforms, the different forms of a protein with sequence variations including post-translational modifications (PTMs), execute vital functions in biological systems such as cell signaling and epigenetic regulation. Precisely defining the stoichiometry of PTMs has been challenging because, in the widely used bottom-up proteomics methods, the detection occurs at the peptide level and thus the link between peptides and their specific modification site is lost, resulting in proteoform ambiguity. Advances in top-down mass spectrometry (MS) technology have permitted the direct characterization of intact proteoforms and their exact number of modification sites, allowing for the relative quantification of positional isomers (PI). Proteins with positional isomers refers to proteoforms with identical total mass and set of modifications but varying PTM site combinations. The relative abundance of PI can be estimated by matching proteoform-specific fragment ions to top-down tandem MS (MS2) data to localize and quantify modifications. However, current approaches heavily rely on manual annotation. Here, we present IsoForma, an open-source R package for relative quantification of PI within a single tool. We benchmarked IsoForma’s performance against two existing workflows and highlight the similarity of the results and improvements in speed. Overall, IsoForma provides a streamlined process, reduces the time of conducting isoform-based analyses, and offers an essential framework for developing customized proteoform analysis workflows. Finally, the software is open source and available at https://github.com/EMSL-Computing/isoforma-lib.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Isomers and band assignments in the cryogenic vibrational spectrum of the binary complex between water and protonated formic acid using two color, IR–IR photobleaching and H/D isotopic substitution

Protonated formic acid (PFA) is purported to be the active species in the catalytic activation of condensation reactions at the acidic interface of microdroplets. Here, we investigate the fundamental interaction between PFA and water with cryogenic ion vibrational spectroscopy of the binary PFA–H 2 O complexes generated via electrospray ionization followed by buffer gas cooling to about 20 K. The patterns displayed by the isomer-specific IR spectra of D 2 -tagged PFA–H 2 O indicate that two distinct, non-interconverting rotamers are present at low temperatures based on the cis and trans structures of the HCO 2 $H$$^{+}_{2}$ core ion. Both of these occur with the water molecule attached to the OH that is in a cis-configuration relative to the CH group (denoted E), but differ in the E vs Z (cis vs trans relative to the CH group) orientation of the spectator OH. This assignment scheme corrects a previous theoretical analysis that invoked a scenario in which structures with E- and Z-bound water molecules interconvert at low (20 K) temperatures. Isomer-specific bands arising from the OH stretches and water bending modes are deconvoluted using isotopomer-specific spectroscopy of the complexes with partial H/D exchange. The dependence of the nominal shared proton OH stretch frequency on the deuteration of the tethered water confirms strong coupling between this mode and the water bending fundamental.

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

Spin-trap isomers in deformed, odd-odd nuclei in the light rare-earth region near $N=98$

Masses of neutron-rich, odd-odd Pm, Eu, and Tb nuclei near N = 98 were measured using the Canadian Penning Trap mass spectrometer at the Californium Rare Isotope Breeder Upgrade (CARIBU) facility. High-resolution mass measurements yielded the discovery of spin-trap isomers at N = 97 in Tb 162 , and in the N = 99 isotones of Pm 160 and Tb 164 . Furthermore, no evidence of long-lived isomers were observed at N = 95 in Eu 158 , at N = 97 in Pm 158 , nor at N = 101 in Eu 164 and Tb 166 . Here, these experimental observations are compared to results from multiquasiparticle blocking calculations.

150 ≤ A ≤ 189↗
DOE OSTI2023

Interesting Isomers - From classic nuclear physics to dark matter - [Slides]

The physics of isomers is almost a century old. While a lot of isomers are studied, the most extreme cases remain unexplored. Testing classic nuclear physics in the extrema. A door into dark sector that is allows us to look for DM types that are not accessible in larger efforts.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗