Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Isomerism”

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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Measurements of Intermediate Species in Fuel-Rich Oxidation of Ethylene, Toluene, and n -Decane

Polycyclic aromatic hydrocarbons (PAHs) are important precursors to the formation of soot and are also pollutant emissions from combustion devices, including internal combustion engines. To understand the formation of PAHs, the low-molecular-weight hydrocarbon chemistry leading to their formation needs to be understood. Toward this goal, fuel-rich oxidation of three different hydrocarbons, i.e., ethylene, toluene, and n-decane, has been investigated in an atmospheric pressure flow reactor at varying temperatures (1000–1350 K), equivalence ratios (φ = 3.0–12.0), and residence times of 0.25–1.5 s. The major C 1 to C 7 intermediates, such as methane, acetylene, ethylene, allene, propyne, propylene, vinylacetylene, 1,3-butadiene, cyclopentadiene, benzene, and toluene, were quantified using a gas chromatograph equipped with a flame ionization detector. The experimental tendency of intermediate species formation, e.g., the dependence of temperature, equivalence ratio, and residence time, was similar in ethylene oxidation and n-decane oxidation. The concentrations of intermediate species up to C 4 were higher in ethylene/n-decane oxidation than toluene oxidation, while a nearly equal or larger amount of C5–C7 species was produced in toluene oxidation. The experimental data were compared with modeling results using a detailed chemical kinetic mechanism. The calculated data using the kinetic model were in agreement with the experimental results. Additionally, a comprehensive kinetic analysis on the reaction pathways of each species was conducted to assess the differences in the oxidation chemistry with the change in the structure of hydrocarbons. In particular, in-depth analysis of benzene formation was performed, elucidating that two benzene formation pathways were important in ethylene and n-decane oxidation: (1) H elimination of the 2,4-cyclohexadienyl radical produced from the isomerization of the 2,4-cyclopentadienylmethyl radical, and (2) dehydrogenation of cyclohexadiene produced from reactions of vinyl radical with 1,3-butadiene. In toluene oxidation, it was found that benzene was primarily produced from toluene through the replacement of the methyl group with hydrogen.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Relating Molecular Properties to the Persistence of Marine Dissolved Organic Matter with Liquid Chromatography–Ultrahigh-Resolution Mass Spectrometry

Marine dissolved organic matter (DOM) contains a complex mixture of small molecules that eludes rapid biological degradation. Spatial and temporal variations in the abundance of DOM reflect the existence of fractions that are removed from the ocean over different time scales, ranging from seconds to millennia. However, it remains unknown whether the intrinsic chemical properties of these organic components relate to their persistence. Here, we elucidate and compare the molecular compositions of distinct DOM fractions with different lability along a water column in the North Atlantic Gyre. Our analysis utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry at 21 T coupled to liquid chromatography and a novel data pipeline developed in CoreMS that generates molecular formula assignments and metrics of isomeric complexity. Clustering analysis binned 14 857 distinct molecular components into groups that correspond to the depth distribution of semilabile, semirefractory, and refractory fractions of DOM. The more labile fractions were concentrated near the ocean surface and contained more aliphatic, hydrophobic, and reduced molecules than the refractory fraction, which occurred uniformly throughout the water column. These findings suggest that processes that selectively remove hydrophobic compounds, such as aggregation and particle sorption, contribute to variable removal rates of marine DOM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Methane Generation from CO 2 with a Molecular Rhenium Catalyst

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C 1 –C n products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole ( quin-1-oxa ), 2-(quinolin-2-yl)-4,5-dihydrooxazole ( quin-2-oxa ), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole ( quin-3-oxa ) that catalyze the reduction of CO 2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO) 3 Cl ( 1 ), Re(quin-2-oxa)(CO) 3 Cl ( 2 ), and Re(quin-3-oxa)(CO) 3 Cl ( 3 ) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO 2 to CO and CH 4 . When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc +/0 ) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using 13 CO 2 atmosphere produce 13 CH 4 ( m / z = 17) confirming that methane originates from CO 2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e – /8H + reduction of CO 2 to CH 4 . Overall, a ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH 4 . Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH 4 from CO 2 .

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

Double Intramolecular 1,2 C–H Addition of o -Methyl Groups To Form Ruthenium Pincer Double Tuck-In Complexes

Ruthenium pincer complexes have a rich history of coordination and reaction chemistries. In this work, we report our discoveries of previously unreported Ru pincer coordination geometries. We found that mono tuck-in κ 4 -ArPN H PRuLCl complexes react with NaN(SiMe 3 ) 2 producing double tuck-in mer-κ 5 -ArPN H PRuL complexes. Interestingly, when κ 4 -MesPN H PRuCl is dehydrohalogenated, the resulting double tuck-in complex binds N 2 , forming the nitrogen complex κ 5 -MesPN H PRuN 2 . Further, the mer-κ 5 -ArPN H PRuL complexes thermally isomerize to the fac-κ 5 -ArPN H PRuL isomers, which is an uncommon reaction for pincer complexes. The mer-κ 5 -ArPN H PRuL complexes react with CO and CO 2 to form amide κ 4 -ArPN H PRu(CO)L or carbamate κ 5 -ArPN(CO 2 )PRuL complexes, respectively, supporting the hypothesis that the κ 4 -ArPNPRuL amide intermediates are accessible and reactive.

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

Butyltin Keggin Ion with a Rare Four-Coordinate Ca Center

Alkyltin clusters are exploited in nanolithography for the fabrication of microelectronics. The alkyltin Keggin family is unique among Keggin clusters across the periodic table; its members appear to favor the lower-symmetry β and γ isomers rather than the highly symmetrical α and ε isomers. Therefore, the alkyltin Keggin family may provide important fundamental information about the formation and isomerization of Keggin clusters. In this study, we have synthesized and structurally characterized a new butyltin Keggin cluster with a tetrahedral Ca 2+ center, fully formulated [(BuSn) 12 (CaO 4 )(OCH 3 ) 12 (O) 4 (OH) 8 ] 2+ (β-CaSn 12 ). The synthesis is a simple one-step process. Extensive solution characterization including electrospray ionization mass spectrometry, small-angle X-ray scattering, and multinuclear ( 1 H, 13 C, and 119 Sn) nuclear magnetic resonance shows β-CaSn 12 is essentially phase-pure and stable. This differs from the previously reported Na-centered analogues that always form a mixture of β and γ isomers, with facile interconversion. Therefore, this study has clarified prior confusion over complex spectroscopic and crystallographic characterization of the Na-centered analogues. Density functional theory calculations showed the following stability order: γ-CaSn 12 < γ-NaSn 12 < β-CaSn 12 < β-NaSn 12 . The β analogue is always more stable than the γ analogue, consistent with experiment. Notable outcomes of this study include a rare tetrahedral Ca coordination, a Na-free alkyltin cluster (important for microelectronics manufacturing), and a better understanding of Keggin families built of different metal cations.

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

Coupled Electronic and Nuclear Motions during Azobenzene Photoisomerization Monitored by Ultrafast Electron Diffraction

Ultrafast electron diffraction is a powerful technique that can resolve molecular structures with femtosecond and angstrom resolutions. We demonstrate theoretically how it can be used to monitor conical intersection dynamics in molecules. Specific contributions to the signal are identified which vanish in the absence of vibronic coherence and offer a direct window into conical intersection paths. A special focus is on hybrid scattering from nuclei and electrons, a process that is unique to electron (rather than X-ray) diffraction and monitors the strongly coupled nuclear and electronic motions in the vicinity of conical intersections. Furthermore, an application is made to the cis to trans isomerization of azobenzene, computed with exact quantum dynamics wavepacket propagation in a reactive two-dimensional nuclear space.

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

Polynomial Scaling Localized Active Space Unitary Selective Coupled Cluster Singles and Doubles

We present a polynomial-scaling algorithm for the localized active space unitary selective coupled cluster singles and doubles (LAS-USCCSD) method. In this approach, cluster excitations are selected based on a threshold ϵ determined by the absolute gradients of the LAS-UCCSD energy with respect to cluster amplitudes. Using the generalized Wick’s theorem for multireference wave functions, we derive the gradient expression as a polynomial function of one-, two-, and three-body reduced density matrices and 1- and 2-electron integrals, valid for any multireference wave function. The resulting gradient implementation exhibits a memory scaling of 𝒪(N 6 ), with N spin orbitals in the combined active space of all fragments. The variational quantum eigensolver is used to optimize the selected cluster excitations on a quantum simulator. Furthermore, by plotting the energy error, defined as the difference between the LAS-USCCSD and corresponding CASCI energies, against the inverse cluster amplitude selection threshold (ϵ –1 ) for polyene chains containing 2 to 5 π-bond units, we establish a relationship between the energy error and the threshold. To further validate the accuracy of LAS-USCCSD, we computed the cis–trans isomerization energy of stilbene (a 20-qubit system) and the magnetic coupling constant of the tris-hydroxo-bridged chromium dimer [Cr 2 (OH) 3 (NH 3 ) 6 ] 3+ (evaluated as both 12- and 20-qubit systems) using the Qiskit-Qulacs simulator. Assessing such examples is important to determine the practical feasibility of quantum simulations for chemically realistic systems. Toward this goal, with the LAS-USCCSD algorithm we estimated the quantum resources required for simulating an active space of (30e,22o) in [Cr 2 (OH) 3 (NH 3 ) 6 ] 3+ , a size that remains beyond the reach of current quantum simulators for accurate treatment.

Algorithms↗
DOE OSTI2020

Strong, Nonresonant Radiation Enhances Cis–Trans Photoisomerization of Stilbene in Solution

Previously, it has been demonstrated that external electric fields may be used to exert control over chemical reactivity. In this paper, the impact of a strong, nonresonant IR field (1064 nm) on the photoisomerization of cis-stilbene is investigated in cyclohexane solution. The design of a suitable reaction vessel for characterization of this effect is presented. The electric field supplied by the pulsed, near-IR radiation (ε 1 = 4.5 × 10 7 V/cm) enhances the cis → trans photoisomerization yield at the red edge of the absorption spectrum (wavelengths between 337 and 340 nm). Within the microliter focal volume, up to 75% of all cis-stilbene molecules undergo isomerization to trans-stilbene in the strong electric-field environment, indicating a significant increase relative to the 35% yield of trans-stilbene under field-free conditions. This result correlates with a 1–3% enhancement in the trans-stilbene concentration throughout the bulk solution. Theoretical analysis suggests that the observed change is the result of dynamic Stark shifting of the ground and first excited states, leading to a significant redshift in cis-stilbene’s absorption spectrum. The predicted increase in the absorption cross section in this range of excitation wavelengths is qualitatively consistent with the experimental increase in trans-stilbene production.

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

Transformation of an Embedded Five-Membered Ring in Polycyclic Aromatic Hydrocarbons via the Hydrogen-Abstraction–Acetylene-Addition Mechanism: A Theoretical Study

Five-membered rings are constituents of many polycyclic aromatic hydrocarbons (PAHs) and their presence on the edges of large PAHs has been repeatedly observed experimentally. However, modern kinetic combustion models often do not consider the growth of PAHs through the transformation of the five-membered rings. Here, in connection with the above, we carried out a theoretical study of the mechanism of Hydrogen-Abstraction-aCetylene-Addition (HACA) transformation of an embedded five-membered ring on the armchair PAH edge to a six-membered ring, considering cyclopenta[d,e,f]phenanthrene (4,5-methylenephenanthrene) as a prototype system for this process. The potential energy surface for the reactions of cyclopenta[d,e,f]phenanthrenyl radicals produced by direct H abstractions from cyclopenta[d,e,f]phenanthrene with acetylene has been compiled at the G3(MP2,CC)//B3LYP/6-311G(d,p) level of theory including zero-point vibrational energy corrections. The computed energies and molecular parameters were then used to solve the Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) in order to calculate reaction rate at various pressures and temperatures, which were fitted to modified Arrhenius equation for further kinetic modeling. The results show that the HACA transformation of the embedded five-membered ring to a six-membered ring is possible, albeit slow. The most viable reaction mechanism involves the R2 + C 2 H 2 reaction, where the acetylene molecules adds to a σ-radical in the six-membered ring adjacent to the five-membered ring via a low entrance barrier. The predominant product of R2 + C 2 H 2 is predicted to be 3 ethynyl 4H cyclopenta[def]phenanthrene Pr5 via immediate H elimination from the initial addition complex. Next, Pr5 undergoes H-assisted isomerization to 4aH-pentaleno[4,3,2,1-cdef]phenanthrene Pr4, and the latter adds an H atom eventually forming the 1-pyrenylmethyl radical Pr3: R2 + C 2 H 2 ⇌ 3 ethynyl 4H cyclopenta[def]phenanthrene (Pr5) + H ⇌ 4aH-pentaleno[4,3,2,1-cdef]phenanthrene (Pr4) + H Pr5 + H ⇌ Pr4 + H Pr4 + H → 1-pyrenylmethyl (Pr3) This HACA sequence may be competitive with the methyl radical addition to the R1 radical formed by H abstraction from the CH 2 group in the five-membered ring of cyclopenta[d,e,f]phenanthrene, which provides a pathway to pyrene following two H atom losses. Relative contributions of the two mechanisms of the five- to six-membered ring transformation would strongly depend on the branching ratios of the R1 and R2 radicals produced by the H abstractions and the available concentration of C 2 H 2 vs. CH 3 and hence differ in different flames.

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

Quantitative Detection of Products and Radical Intermediates in Low-Temperature Oxidation of Cyclopentane

We present a combined experimental and theoretical investigation of the autoignition chemistry of a prototypical cyclic hydrocarbon, cyclopentane. Experiments using a high-pressure photolysis reactor coupled to time-resolved synchrotron VUV photoionization mass spectrometry directly probe the short-lived radical intermediates and products in cyclopentane oxidation reactions. We detect key peroxy radical intermediates ROO and OOQOOH, as well as several hydroperoxides, formed by second O 2 addition. Automated quantum chemical calculations map out the R + O 2 + O 2 reaction channels and demonstrate that the detected intermediates belong to the dominant radical chain-branching pathway: ROO (+ O 2 ) → γ-QOOH + O 2 → γ-OOQOOH → products. ROO, OOQOOH, and hydroperoxide products of second-O 2 addition undergo extensive dissociative ionization, making their experimental assignment challenging. We use photoionization dynamics calculations to aid in their characterization and report the absolute photoionization spectra of isomerically pure ROO and γ-OOQOOH. Here, a global statistical fit of the observed kinetics enables reliable quantification of the time-resolved concentrations of these elusive, yet critical species, paving the way for detailed comparisons with theoretical predictions from master-equation-based models.

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

Photodissociation and Infrared Spectroscopy of Uranium–Nitrogen Cation Complexes

Laser vaporization of uranium in a pulsed supersonic expansion of nitrogen is used to produce complexes of the form U + (N 2 ) n (n = 1–8). These ions are mass selected in a reflectron time-of-flight spectrometer and studied with visible and UV laser fixed-frequency photodissociation and with tunable infrared laser photodissociation spectroscopy. The dissociation patterns and spectroscopy of U + (N 2 ) n indicate that N 2 ligands are intact molecules and that there is no insertion chemistry resulting in UN + or NUN + . Fixed frequency photodissociation at 532 and 355 nm indicate that the U + –N 2 bond dissociation energy varies little with changing coordination. The photon energy and the number of ligands eliminated allow an estimate of the average U + –N 2 dissociation energy of 12 kcal/mol. Infrared bands are observed for these complexes near the N–N stretch vibration via elimination of N 2 molecules. These resonances are observed to be shifted about 130 cm–1 to the red from the free-N 2 frequency for complexes with n = 3–8. Density functional theory indicates that U + is most stable in the sextet state in these complexes and that N 2 molecules bind in end-on configurations. Furthermore, the fully coordinated complex is predicted to be U + (N 2 ) 8 , which has a cubic structure. The vibrational frequencies predicted by theory are consistently lower than those in the experiment, independent of the isomeric structure or spin state of the complexes. Despite its failure to reproduce the infrared spectra, theory provides an average U + –N 2 dissociation energy of 11.8 ± 0.5 kcal/mol, in good agreement with the value from the experiments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Theoretical Study of the Reaction of the Methylidyne Radical (CH; X 2 Π) with 1-Butyne (CH 3 CH 2 CCH; X 1 A')

In this study, ab initio CCSD(T)-F12/cc-pVTZ-f12//ωB97X-D/6-311G(d,p) + ZPE(ωB97X-D/6-311G(d,p)) calculations were carried out to unravel the area of the C 5 H 7 potential energy surface accessed by the reaction of the methylidyne radical with 1-butyne. The results were utilized in Rice-Ramsperger-Kassel-Marcus calculations of the product branching ratios at the zero pressure limit. The preferable reaction mechanism has been shown to involve (nearly) instantaneous decomposition of the initial reaction adducts, whose structures are controlled by the isomeric form of the C 4 H 6 reactant. If CH adds to the triple CΞC bond in the entrance reaction channel, the reaction is predicted to predominantly form the methylenecyclopropene + methyl (CH 3 ) and cyclopropenylidene + ethyl (C 2 H 5 ) products roughly in a 2:1 ratio. CH insertion into a C-H bond in the methyl group of 1-butyne is anticipated to preferentially form ethylene + propargyl (C 3 H 3 ) by the C-C bond β-scission in the initial complex, whereas CH insertion into C-H of the CH 2 group would predominantly produce vinylacetylene + methyl (CH 3 ) also by the C-C bond β-scission in the adduct. The barrierless and highly exoergic CH + 1-butyne reaction, facile in cold molecular clouds, is not likely to lead to the carbon skeleton molecular growth but generates C 4 H 4 isomers methylenecyclopropene, vinylacetylene, and 1,2,3-butatriene and smaller C 2 and C 3 hydrocarbons such as methyl, ethyl, and propargyl radicals, ethylene, and cyclopropenylidene.

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

A Conical Intersection Influences the Ground State Rearrangement of Fulvene to Benzene

The rearrangement of fulvene to benzene is believed to play an important role in the formation of soot during hydrocarbon combustion. Previous work has identified two possible mechanisms for the rearrangement-a unimolecular path and a hydrogen-atom-assisted, bimolecular path. Computational results to date have suggested that the unimolecular mechanism faces a barrier of about 74 kcal/mol, which makes it unable to compete with the bimolecular mechanism under typical combustion conditions. This computed barrier is about 10 kcal/mol higher than the experimental value, which is an unusually large discrepancy for modern electronic structure theory. In the present work, we have reinvestigated the unimolecular mechanism computationally, and we have found a second transition state that is approximately 10 kcal/mol lower in energy than the previously identified one and, therefore, in excellent agreement with the experimental value. The existence of two transition states for the same rearrangement arises because there is a conical intersection between the two lowest singlet states which occurs in the vicinity of the reaction coordinates. The two possible paths around the cone on the lower adiabatic surface give rise to the two distinct saddle points. The lower barrier for the unimolecular mechanism now makes it competitive with the bimolecular one, according to our calculations. In support of this conclusion, we have reanalyzed some previous experimental results on anisole pyrolysis, which leads to benzene as a significant product and have shown that the unimolecular and bimolecular mechanisms for fulvene ? benzene must be occurring competitively in that system. Finally, we have identified that similar conical intersections arise during the isomerizations of benzofulvene and isobenzofulvene to naphthalene.

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

The Role of Methylaryl Radicals in the Growth of Polycyclic Aromatic Hydrocarbons: The Formation of Five-Membered Rings

The regions of the C 13 H 11 potential energy surface (PES) related to the unimolecular isomerization and decomposition of the 1-methylbiphenylyl radical and accessed by the 1-/2-methylnaphthyl + C 2 H 2 reactions have been explored by ab initio G3(MP2,CC)//B3LYP/6-311G(d,p) calculations. The kinetics of these reactions relevant to the growth of polycyclic aromatic hydrocarbons (PAH) under high-temperature conditions in circumstellar envelopes and in combustion flames has been studied employing the RRKM-Master Equation approach. The unimolecular reaction of 1-methylbiphenylyl proceeding via a five-membered ring closure followed by H elimination is predicted to be very fast, on a submicrosecond scale above 1000 K and to result in the formation of an embedded five-membered ring in the 9H-fluorene product. The 1-/2-methylnaphthyl + C 2 H 2 reaction mechanism involves acetylene addition to the radical on the methylene group followed by a six- or five-membered ring closure and aromatization via an H atom loss. Despite of the complexity of the C 13 H 11 PES, these straightforward pathways are dominant in the high-temperature regime (above ~1000 K), with the prevailing products being phenalene, with a significant contribution of 1H-cyclopenta(a)naphthalene, for 1-methylnaphthyl + C 2 H 2 , and 1H-cyclopenta(b)naphthalene and 3H-cyclopenta(a)naphthalene, for 2-methylnaphthyl + C 2 H 2 . The methylnaphthyl reactions with acetylene represent a clean source of the three-ring PAHs, but they are relatively slow owing to the high entrance barriers of ~10 kcal/mol, with the rate constants of about an order of magnitude lower as compared to those for naphthyl + allene and σ-aryl + C 2 H 2 . Here, the 1-methylnaphthyl + C 2 H 2 and 2-methylnaphthyl + C 2 H 2 reactions represent prototypes for PAH growth by an extra six- and five-membered ring on a zigzag edge or a corner of PAH and the generated modified Arrhenius expressions are recommended for kinetic modeling of PAH expansion by the mechanism of acetylene addition to methylaryl radicals.

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

Conformational Changes Induced by Methyl Side-Chains in Protonated Tripeptides Containing Glycine and Alanine Residues

We present a systematic study of the conformational and isomeric populations in gas-phase protonated tripeptides containing glycine and alanine residues using infrared predissociation spectroscopy of cryogenically cooled ions. Specifically, the protonated forms of Gly-Gly-Gly, Ala-Gly-Gly, Gly-Ala-Gly, Gly-Gly-Ala, Ala-Ala-Gly, Ala-Gly-Ala, Gly-Ala-Ala, and Ala-Ala-Ala allow us to sample all permutations of the methyl side-chain position, providing a comprehensive view of the effects of this simple side-chain on the 3-D structure of the peptide. The individual structural populations for all but one of these peptide species are determined via conformer-specific IR–IR double-resonance spectroscopy and comparison with electronic structure predictions. The observed structures can be classified into three main families defined by the protonation site and the number of internal hydrogen bonds. The relative contribution of each structural family is highly dependent on the exact amino acid sequence of the tripeptide. Here, these observed changes in structural population can be rationalized in terms of the electron-donating effect of the methyl side-chain modulating the local proton affinities of the amine and various carbonyl groups in the tripeptide.

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

Inelastic Neutron Scattering from Thin Film Biaxially Oriented Polyethylene Terephthalate

Recent interest in emerging processes for polymer manufacturing and bio-based chemistries for direct chemical recycling/upcycling has motivated new research focused on a deeper understanding of atomic-scale polymer properties and how they influence macroscopic phenomena. Uncovering the fundamental properties of polymers that give rise to macroscopic behavior could enable new pathways for improved recyclability or utilization of alternative “greener” polymer analogues. In this study, the neutron vibrational spectrum was measured for a film of biaxially oriented polyethylene terephthalate (BoPET) using inelastic neutron scattering (INS), to investigate the relationship between the structure and dynamics of a widely used polymer. Compared to conventional spectroscopic techniques, the use of INS is advantageous for polymeric materials due to the absence of selection rules (i.e., all transitions are allowed), broad-band energy range, and considerable sensitivity to hydrogen modes. In order to distinguish the vibrational modes caused by trans and gauche rotational isomerism, the normal modes of vibration were calculated from a density functional theory-optimized structure of crystalline PET (cPET), representative of the all-trans state, and compared with INS from “highly crystalline” PET powder. Although in- and out-of-plane wagging of hydrogens on the ring structure exhibit significant contribution to both BoPET and cPET spectra, the wagging, rocking, and twisting modes of hydrogen on the ethylene glycol group are, in most cases, conformation-specific. These results were further rationalized by investigating the role of hyperconjugation in stabilizing both conformations using the natural bond order method. Here, through comparison of experimental and calculated INS results, this work provides the fundamental basis for discovering the role of structure and dynamics in shaping the macroscopic properties of PET and polymer analogues.

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

Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers

The 2-butenal oxide Criegee intermediate [(CH 3 CH=CH)CHOO], an isomer of the four-carbon unsaturated Criegee intermediates derived from isoprene ozonolysis, is characterized on its first π * ←π electronic transition and by the resultant dissociation dynamics to O ( 1 D) + 2-butenal [(CH 3 CH=CH)CHO] products. The electronic spectrum of 2-butenal oxide under jet-cooled conditions is observed to be broad and unstructured with peak absorption at 373 nm, spanning to half maxima at 320 and 420 nm, and in good accord with the computed vertical excitation energies and absorption spectra obtained for its lowest energy conformers. The distribution of total kinetic energy released to products is ascertained through velocity map imaging of the O ( 1 D) products. About half of the available energy, deduced from the theoretically computed asymptotic energy, is accommodated as internal excitation of the 2-butenal fragment. A reduced impulsive model is introduced to interpret the photodissociation dynamics, which accounts for the geometric changes between 2-butenal oxide and the 2-butenal fragment, and vibrational activation of associated modes in the 2-butenal product. Application of the reduced impulsive model to the photodissociation of isomeric methyl vinyl ketone oxide reveals greater internal activation of the methyl vinyl ketone product arising from methyl internal rotation and rock, which is distinctly different than the dissociation dynamics of 2-butenal oxide or methacrolein oxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Energetic and Spectroscopic Properties of Astrophysically Relevant MgC 4 H Radicals Using High-Level Ab Initio Calculations

Considering the importance of magnesium-bearing hydrocarbon molecules (MgC n H; n = 2, 4, and 6) in the carbon-rich circumstellar envelopes (e.g., IRC+10216), a total of 28 constitutional isomers of MgC 4 H have been theoretically investigated using density functional theory (DFT) and coupled-cluster methods. The zero-point vibrational energy corrected relative energies at the ROCCSD(T)/cc-pCVTZ level of theory reveal that the linear isomer, 1-magnesapent-2,4-diyn-1-yl (1, 2 Σ + ), is the global minimum geometry on the MgC 4 H potential energy surface. The latter has been detected both in the laboratory and in the evolved carbon star, IRC+10216. The calculated spectroscopic data for 1 match well with the experimental observations (error ~ 0.78%) which validates our theoretical methodology. Plausible isomerization processes happening among different isomers are examined using DFT and coupled-cluster methods. CASPT2 calculations have been performed for a few isomers exhibiting multireference characteristics. The second most stable isomer, 1-ethynyl-1λ 3 -magnesacycloprop-2-ene-2,3-diyl (2, 2 A 1 , μ = 2.54 D), is 146 kJ mol –1 higher in energy than 1 and possibly the next promising candidate to be detected in the laboratory or in the interstellar medium in future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗