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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 109 records · Page 6
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DOE OSTI2023

OH Roaming during the Ozonolysis of α-Pinene: A New Route to Highly Oxygenated Molecules?

The formation of low-volatility organic compounds in the ozonolysis of α-pinene, the dominant atmospheric monoterpene, provides an important route to aerosol formation. Here, in this work, we consider a previously unexplored set of pathways for the formation of highly oxygenated molecules in α-pinene ozonolysis. Pioneering, direct experimental observations of Lester and co-workers have demonstrated a significant production of hydroxycarbonyl products in the dissociation of Criegee intermediates. Theoretical analyses indicate that this production arises from OH roaming-induced pathways during the OO fission of the vinylhydroperoxides (VHPs), which in turn come from internal H transfers in the Criegee intermediates. Ab initio kinetics computations are used here to explore the OH roaming-induced channels that arise from the ozonolysis of α-pinene. For computational reasons, the calculations consider a surrogate for α-pinene, where two spectator methyl groups are replaced with H atoms. Multireference electronic structure calculations are used to illustrate a variety of energetically accessible OH roaming pathways for the four VHPs arising from the ozonolysis of this α-pinene surrogate. Ab initio transition-state theory-based master equation calculations indicate that for the dissociation of stabilized VHPs, these OH roaming pathways are kinetically significant with a branching that generally increases from ~20% at room temperature up to ~70% at lower temperatures representative of the troposphere. For one of the VHPs, this branching already exceeds 60% at room temperature. For the overall ozonolysis process, these branching ratios would be greatly reduced by a limited branching to the stabilized VHP, although there would also be some modest roaming fraction for the nonthermal VHP dissociation process. The strong exothermicities of the roaming-induced isomerizations/additions and abstractions suggest new routes to fission of the cyclobutane rings. Such ring fissions would facilitate further autoxidation reactions, thereby providing a new route for producing highly oxygenated nonvolatile precursors to aerosol formation.

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

Theoretical Kinetics Predictions for Reactions on the NH 2 O Potential Energy Surface

Recent modeling studies of ammonia oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies among the existing literature mechanisms. In this study, high-level theoretical kinetics predictions have been obtained for reactions on the NH 2 O potential energy surface, including the NH 2 + O, HNO + H, and NH + OH reactions. These reactions have previously been highlighted as important reactions in NH 3 oxidation with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations, including large basis sets and high-level corrections to yield high-accuracy (~0.2 kcal/mol 2σ uncertainty) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature- and pressure-dependent kinetics. For radical–radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constants as well as the branching ratios. We find that the NO + H 2 channel contributes 10% of the total NH 2 + O flux at combustion temperatures, although this channel is not included in modern NH 3 oxidation mechanisms. Modeling is used to illustrate the ramifications of these rate predictions on the kinetics of NH 3 oxidation and NO x formation. Finally, the present results for NH 2 + O are important for predicting the chain branching and formation of NO in the oxidation of NH 3 and thermal DeNO x .

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↗
DOE OSTI2024

Quasi-Classical Trajectory Calculation of Rate Constants Using an Ab Initio Trained Machine Learning Model (aML-MD) with Multifidelity Data

Machine learning (ML) provides a great opportunity for the construction of models with improved accuracy in classical molecular dynamics (MD). However, the accuracy of a ML trained model is limited by the quality and quantity of the training data. Generating large sets of accurate ab initio training data can require significant computational resources. Furthermore, inconsistent or incompatible data with different accuracies obtained using different methods may lead to biased or unreliable ML models that do not accurately represent the underlying physics. Recently, transfer learning showed its potential for avoiding these problems as well as for improving the accuracy, efficiency, and generalization of ML models using multifidelity data. In this work, ab initio trained ML-based MD (aML-MD) models are developed through transfer learning using DFT and multireference data from multiple sources with varying accuracy within the Deep Potential MD framework. Further, the accuracy of the force field is demonstrated by calculating rate constants for the H + HO 2 → H 2 + 3 O 2 reaction using quasi-classical trajectories. We show that the aML-MD model with transfer learning can accurately predict the rate constants while reducing the computational cost by more than five times compared to the use of more expensive quantum chemistry training data sets. Hence, the aML-MD model with transfer learning shows great potential in using multifidelity data to reduce the computational cost involved in generating the training set for these potentials.

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

Nonunitary Variational Quantum Eigensolver with the Localized Active Space Method and Cost Mitigation

Accurately describing strongly correlated systems with affordable quantum resources remains a central challenge for quantum chemistry applications on near and intermediate term quantum computers. The localized active space self-consistent field (LASSCF) approximates the complete active space self-consistent field (CASSCF) by generating active space-based wave functions within specific fragments while treating interfragment correlation with mean-field approach, hence is computationally less expensive. Hardware-efficient ansatzes (HEA) offer affordable and shallower circuits, yet they often fail to capture the necessary correlation. Previously, Jastrow-factor-inspired nonunitary qubit operators were proposed to use with HEA for variational quantum eigensolver (VQE) calculations (so-called nuVQE), as they do not increase circuit depths and recover correlation beyond the mean-field level for Hartree–Fock initial states. Here, in this study, we explore running nuVQE with LASSCF as the initial state. The method, named LAS-nuVQE, is shown to recover interfragment correlations, reach chemical accuracy with a small number of gates (<70) in both H 4 and square cyclobutadiene (C 4 H 4 ), and produces more accurate energetics than its HEA counterparts at all circuit depths. To further address the inherent symmetry-breaking in HEA, we implemented spin-constrained LAS-nuVQE to extend the capabilities of HEA further and show spin-pure results for square cyclobutadiene. We also mitigate the increased measurement overhead of nuVQE via Pauli grouping and shot-frugal sampling, reducing measurement costs by up to 2 orders of magnitude compared to ungrouped operator, and show that one can achieve better accuracy with a small number of shots (10 3–4 ) per one expectation value calculation compared to noiseless simulations with one or two orders of magnitude more shots. Finally, wall clock time estimates show that, with our measurement mitigation protocols, nuVQE becomes a cheaper and more accurate alternative than vanilla VQE with HEA. Taken together, these developments illustrate a practical pathway toward performing multireference chemical simulations with accuracy and affordable resources on today’s quantum hardware, achieving both accuracy and affordability in challenging correlated systems.

Wang, Qiaohong [Univ. of Chicago, IL (United State↗
DOE OSTI2025

The Reaction Rates of Amidogen and Ammonia with Nitrous Oxide: Implications for Combustion Mechanisms

Pulsed laser photolysis experiments with laser-induced fluorescence detection of NH 2 set an upper limit to the rate constant for reaction with N 2 O of k < 1 × 10 −15 cm 3 molecule −1 s −1 at 513 K. Computations were based on geometries and anharmonic frequency analysis (B2PLYP-D3/cc-pVTZ) followed by coupled cluster calculations extrapolated to the infinite basis set limit, with corrections for core−valence electron correlation, scalar relativistic effects, and correlation up to CCSDT(Q). Species that showed multireference character were quantified with MRCI(7,7)+Q/cc-pVTZ theory. Rate constants were obtained for the dominant product channel H 2 NN + NO, along with HN 3 + OH, H 2 NO + N 2 , NNH + HNO, ON(NH) 2 and HNNH + NO. The last channel is slow even at 2500 K, contrary to an early empirical estimate and confirming recent suggestions. Modeling of literature experiments on oxidation of NH 3 by N 2 O shows that all channels are too slow to make a significant impact on the loss of N 2 O in ammonia flames. Similarly, the direct NH 3 + N 2 O reaction is found to be negligibly slow.

Ammonia↗
DOE OSTI2026

Thorium Monosilicide, ThSi: An Experimental and Theoretical Study

The present theoretical and experimental combination study investigates the ThSi molecule in detail. Computationally, we utilized high-level multireference and coupled-cluster levels of theory conjoined with large correlation consistent basis sets to study a series of electronic and spin–orbit states of ThSi. Here, we report potential energy curves (PECs), electron configurations at equilibrium distances, spectroscopic constants, energetics, and spin–orbit coupling effects for 16 electronic states of ThSi. The studied 16 electronic states are arranged tightly within 0.9 eV, highlighting the complexity of the electronic spectrum of ThSi. The ground electronic state of ThSi is a single-reference 1 1 Σ + state that derives from the 1σ 2 2σ 2 1π 4 electronic configuration. The Ω = 0 + spin–orbit ground state of ThSi is composed of 1 1 Σ + (47%) and 13Π (44%) electronic states. Our measured bond energy (D0) of ThSi, obtained using resonant two-photon ionization (R2PI) spectroscopy is 3.146(4) eV, where the assigned error limit is given in parentheses in units of the last quoted digits. The computed D0 of ThSi (Ω = 0 + ) at the CBS-C-CCSD(T)-δT(Q)-δDK-δSO level (3.181 eV) is in good agreement with the experimental value. Our derived enthalpy of formation for ThSi, Δ f H 0K o (ThSi(g)), is 971.8(6.0) kJ/mol. Finally, we have performed density functional theory (DFT) calculations for ThSi(1 1 Σ + ) using 16 exchange correlation functionals that span multiple rungs of “Jacob’s ladder” of density functional approximation (DFA) to assess the DFT errors on D 0 , r e , and ω e of ThSi with respect to experimental and ab initio coupled-cluster values.

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

Bond Dissociation Energies of the Actinide Halides AnX, An = Ac–Lr and X = F–I, Utilizing Relativistic Composite Coupled Cluster Approaches

Bond dissociation energies (BDEs) have been calculated for the set of actinide halides AnX with An=Ac, Pa, and Np-Lr and X=F-I. Two composite thermochemistry methods based on the Feller-Peterson-Dixon (FPD) approach have been utilized, one involving spinor-based relativistic CCSD(T) calculations where spin-orbit (SO) was included at the orbital level and another using scalar relativistic CCSD(T) with a posteriori SO contributions based on 2-component multireference configuration interaction calculations. The method that was chosen for a given actinide halide was based on which representation yielded the best single determinant reference determinant for the coupled cluster calculation. The spinor-based method was chosen for all cases except for AmX, CmX, and BkX. Both composite approaches included contributions accounting for basis set truncation, outer-core correlation, the Gaunt interaction, and QED. The scalar FPD results, as well as the spinor-based calculations for AcF, also included higher order electron correlation up through CCSDT(Q). In addition to BDEs, CCSD(T) equilibrium bond lengths, harmonic frequencies, and vibrational anharmonicity constants are reported for all species. Last, the FPD BDEs for the fluorides were used to confirm the trend across the actinide series previously predicted by Gibson using bonding models based atomic promotion energies that provide a single 6d electron for bonding. In particular the local minimum in the BDEs at AmF is confirmed in the present calculations. Furthermore, the BDEs for LrX are predicted to be slightly larger than those of AcX, making them the largest in the actinide halide series.

Actinides↗
DOE OSTI2024

Exploring the Computational Aspects of Propylene Oligomerization Catalysis Using M′ 2 M Type Trimetallic MOF Nodes

Metal-organic frameworks have emerged as promising materials in the field of catalysis. They offer an optimal ground for screening catalysts and tailoring their catalytic properties. Here, in this work, via density functional theory (DFT) calculations, we investigated the catalytic activity of the trimetallic MOF nodes, M' 2 M for propylene oligomerization, by varying the active metal M from Sc to Cu with M' being Fe, aiming to grasp the impact of altering the active atoms on the catalyst's activity. Additionally, we examined how substituting the spectator atom, M', with other transition metals, i.e., from Sc to Cu, affects these energy barriers, keeping Ni as the active metal. We proposed several cases with lower or comparable energy barriers to the experimentally reported Fe 2 Ni trimetallic MOF node. In addition, we found a correlative relationship between spin-density from natural population analysis and energy barriers in the realm of C-C bond formation, whereby an elevation in spin-density is found to be inversely proportional to the magnitude of the energy barriers. Moreover, we calculated the energy barriers for C-C coupling and beta-hydride elimination using multireference NEVPT2 calculations on top of the CASSCF wave function to validate the rate-determining step that is predicted by DFT.

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

Internal Conversion between Bright (1 1 B $^+_u$) and Dark (21 A $^-_g$) States in s- trans -Butadiene and s- trans -Hexatriene

Internal conversion (IC) between the two lowest singlet excited states, 1 1 B$_u^+$ and 2 1 A$_g^–$, of s-trans-butadiene and s-trans-hexatriene is investigated using a series of single- and multi- reference wave function and density functional theory (DFT) methodologies. Three independent types of the equation-of-motion coupled-cluster (EOMCC) theory capable of providing an accurate and balanced description of one- as well as two-electron transitions, abbreviated as δ-CR-EOMCC(2,3), DIP-EOMCC(4h2p){N o }, and DEA-EOMCC(4p2h){N u } or DEA-EOMCC(3p1h,4p2h){N u }, consistently predict that the 1 1 B$_u^+$/2 1 A$_g^–$ crossing in both molecules occurs along the bond length alternation coordinate. However, the analogous 1 1 B$_u^+$ and 2 1 A$_g^–$ potentials obtained with some multireference approaches, such as CASSCF and MRCIS(D), as well as with the linear-response formulation of time-dependent DFT (TDDFT), do not cross. Hence, caution needs to be exercised when studying the low-lying singlet excited states of polyenes with conventional multiconfigurational methods and TDDFT. The multistate many-body perturbation theory methods, such as XMCQDPT 2 , do correctly reproduce the curve crossing. Among the simplest and least expensive computational methodologies, the DFT approaches that incorporate the contributions of doubly excited configurations, abbreviated as MRSF (mixed reference spin-flip) TDDFT and SSR( 4,4 ), accurately reproduce our best EOMCC results. This is highly promising for nonadiabatic molecular dynamics simulations in larger systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Optical Properties of Neutral F Centers in Bulk MgO with Density Matrix Embedding

The optical spectra of neutral oxygen vacancies (F 0 centers) in the bulk MgO lattice are investigated using density matrix embedding theory. The impurity Hamiltonian is solved with the complete active space self-consistent field and second-order n-electron valence state perturbation theory (NEVPT2-DMET) multireference methods. Here, to estimate defect-localized vertical excitation energies at the nonembedding and thermodynamic limits, a double extrapolation scheme is employed. The extrapolated NEVPT2-DMET vertical excitation energy value of 5.24 eV agrees well with the experimental absorption maxima at 5.03 eV, whereas the excitation energy value of 2.89 eV at the relaxed triplet defect-localized state geometry overestimates the experimental emission at 2.4 eV by only nearly 0.5 eV, indicating the involvement of the triplet–singlet decay pathway.

embedding↗
DOE OSTI2024

Unveiling the Redox Noninnocence of Metallocorroles: Exploring K-Edge X-ray Absorption Near-Edge Spectroscopy with a Multiconfigurational Wave Function Approach

X-ray absorption near-edge spectroscopy (XANES) is an advanced technique for probing the local electronic structure of catalysts, effectively identifying the noninnocent nature of ligands in transition-metal complexes. Metallocorroles with noninnocent corrole rings exhibit unusual electronic structures that challenge traditional density functional theory (DFT) methods, necessitating more rigorous approaches to describe electron correlation accurately. We explored K-edge XANES spectra of Fe, Mn, and Co metallocorroles using TDDFT and wave function-based methods. This is the first investigation employing multireference methods, specifically RASSCF, RASPT2, and MC-PDFT, to analyze the redox noninnocent nature of metallocorroles reflected in their XANES spectra. We quantified the noninnocent character of the corrole and the oxidation states of the metals, capturing more than singly excited excitations responsible for the pre-edge peak. Our findings demonstrate the importance of these advanced computational techniques for accurately predicting XANES spectra, providing a reliable understanding of the electronic properties of such complexes. In conclusion, this study offers a new strategy for investigating ligand redox noninnocence via integrated experimental and computational XANES.

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

Anion Photoelectron Spectroscopy and Ab Initio Studies of the UF – Anion

A synergistic anion photoelectron spectroscopic and ab initio computational study of photodetachment of UF – is reported. The measurement determined a vertical detachment energy of 0.63(03) eV, which is consistent with a spinor-based relativistic coupled-cluster CCSD(T) value of 0.61 eV. The complex spectral features due to excited electronic states and vibrational progressions of UF are analyzed and assigned with the help of spin–orbit-coupled multireference perturbation theory and spinor-based relativistic coupled-cluster calculations. UF and UF – are confirmed to be dominated by ionic bonding. Furthermore, the usefulness of the spinor CCSD(T) approach is demonstrated.

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

Linear and Nonlinear X-ray Spectra of Chiral Molecules: X-ray Circular Dichroism, Sum- and Difference-Frequency Generation of Fenchone and Cysteine

Recent advancements in X-ray light sources enable element-sensitive nonlinear spectroscopies for probing molecular chirality. We simulate X-ray absorption spectroscopy, X-ray circular dichroism (XCD), and nonlinear optical/X-ray SFG and DFG (OX SFG/DFG) signals for two prototypical chiral molecules, fenchone and cysteine. Furthermore, our multireference simulations reproduce experimental data and reveal how novel X-ray spectroscopies exploit the site- and element-sensitivity of X-rays to uncover molecular asymmetry. The XCD spectra show strong asymmetries at chiral centers, while distant atoms contribute weaker signals. The OX SFG/DFG signals, under fixed resonant optical excitation, strongly depend on the core and valence excitations. This allows us to introduce two-dimensional (2D) chirality-sensitive valence-core spectroscopy, which provides insight into the overlap between valence orbitals and local molecular asymmetry. Finally, our estimates using realistic laser and X-ray pulse parameters demonstrate that such nonlinear experiments are feasible at XFELs, offering a promising tool for investigating chiral molecules.

Circular dichroism spectroscopy↗
DOE OSTI2021

Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes

Here the low-valent rhenium(I) salt Na[Re(η 5 -Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)-halide and -pseudohalide complexes: Re(X)(η 5 -Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η 5 -Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The 1 H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χ TIP values of 7.41(44) × 10 -4 to 1.50(51) × 10 -3 cm 3 mol -1 . Multireference complete active space self-consistent field (CASSCF) computations incorporating spin-orbit state mixing revealed small energy separations (1.7-3.0 kcal/mol) between thermally isolated ground states and the first excited spin-orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Uranium(II) Arene Complex That Acts as a Uranium(I) Synthon

We report two-electron reduction of the amidate-supported U(III) mono(arene) complex U(TDA) 3 (2) with KC 8 yields the anionic bis(arene) complex [K[2.2.2]cryptand][U(TDA) 2 ] (3) (TDA = N-(2,6-di-isopropylphenyl)pivalamido). EPR spectroscopy, magnetic susceptibility measurements, and calculations using DFT as well as multireference CASSCF methods all provide strong evidence that the electronic structure of 3 is best represented as a 5f 4 U(II) metal center bound to a monoreduced arene ligand. Reactivity studies show 3 reacts as a U(I) synthon by behaving as a two-electron reductant toward I 2 to form the dinuclear U(III)–U(III) triiodide species [K[2.2.2]cryptand][(UI(TDA) 2 ) 2 (μ-I)] (6) and as a three-electron reductant toward cycloheptatriene (CHT) to form the U(IV) complex [K[2.2.2]cryptand][U(η 7 -C 7 H 7 )(TDA) 2 (THF)] (7). The reaction of 3 with cyclooctatetraene (COT) generates a mixture of the U(III) anion [K[2.2.2]cryptand][U(TDA) 4 ] (1-crypt) and U(COT) 2 , while the addition of COT to complex 2 instead yields the dinuclear U(IV)–U(IV) inverse sandwich complex [U(TDA) 3 ] 2 (μ-η 8 :η 3 -C 8 H 8 ) (8). Two-electron reduction of the homoleptic Th(IV) amidate complex Th(TDA) 4 (4) with KC 8 gives the mono(arene) complex [K[2.2.2]cryptand][Th(TDA) 3 (THF)] (5). The C–C bond lengths and torsion angles in the bound arene of 5 suggest a direduced arene bound to a Th(IV) metal center; this conclusion is supported by DFT calculations.

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

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

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

Highly Conjugated Porphyrin Arrays Enable Optical Resolution of Ferromagnetic and Antiferromagnetic Aligned States of the Triplet Exciton and an Incorporated Stable Radical

Well-defined photogenerated molecular spin systems have potential utility in spintronics and quantum information science (QIS). Because molecular magnetic, optical, and electronic properties can be controlled by design, diverse spin systems can be prepared at modest temperatures. Photogenerated molecular spin systems often involve states prepared from the interaction of excitons and charges. Resolving the nature of electron spin alignment in photogenerated spin states described by the coupling of a triplet exciton and a stable radical commonly relies on EPR spectroscopy. Here, we describe ethyne-bridged (porphinato)metal ( PM n ) oligomers that incorporate a macrocycle-bound Cu(II) radical center. Upon photoexcitation of such PM n arrays, a singdoublet ( 2 S 1 ) state is formed; ultrafast internal conversion (IC) then produces a tripdoublet ( 2 T 1 ) state, which undergoes intersystem crossing (ISC) to produce a tripquartet ( 4 T 1 ) state, before relaxation to the ground state ( 2 S 0 ). These highly conjugated Cu(II) radical-containing PMn arrays enable direct observation of copper porphyrin 2 T 1 → 4 T 1 ISC dynamics from the biexponential decay of the near-infrared (NIR) 2,4 T 1 → 2,4 T n transient absorption manifold. Multireference n-electron valence perturbation theory (NEVPT2) computations illuminate how PM n electronic structure controls the relaxation dynamics of these long-lived (>10 ns) electronically excited multiplet states. These studies show that highly conjugated and polarizable porphyrin arrays incorporating stable spin centers provide rare π-delocalized systems where the ferromagnetic and antiferromagnetic alignment between a triplet exciton and a stable radical are both spectrally resolved and addressable using transient optical spectroscopy at wavelengths exceeding 1 μm, providing new opportunities to QIS.

14 SOLAR ENERGY↗