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The molar heat capacity of 1,4-bis(3-methylimidazolium-1-yl)butane bis(trifluoromethylsulfonyl)imide dicationic ionic compound ([C4(MIm)2][NTf2]2) has been studied over the temperature range from 6 to 350 K by adiabatic calorimetry. In the above temperature interval, this compound has been found to form crystal, liquid, and supercooled liquid. For [C4(MIm)2][NTf2]2, the temperature of fusion T°fus = (337.88 ± 0.01) K has been determined by the fractional melting experiments, the enthalpy of fusion ΔfusH° = (52.79 ± 0.28) kJ mol-1 has been measured using the calorimetric method of continuous energy input, and the entropy of fusion ΔfusS° = (156.2 ± 1.7) J K-1 mol-1 has also been evaluated. The standard thermodynamic functions of the studied dicationic ionic compound, namely, the heat capacity Cp°(T), the enthalpy [H°(T) - H°(0)], the entropy S°(T) and the Gibbs free energy [G°(T) - H°(0)] have been calculated on the basis of the experimental data for the temperature range up to 350 K. The results have been discussed and compared with those available in the literature and in the NIST Ionic Liquids Database (ILThermo) for monocationic ionic compounds.

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The occurrence of adiabatic shear bands, as an instability phenomenon, is viewed as a precursor to failure caused by instability at high strain rates. Metastable ß titanium alloys are extensively utilized due to their excellent mechanical properties, which are often subjected to high strain rate loads in service conditions. Understanding and studying their adiabatic shear instability behavior is thus crucial for preventing catastrophic failure and enhancing material performance. In this study via detailed microstructural analyses in the adiabatic shear region of a Ti-10V-2Fe-3Al alloy subjected to high strain rates, it was observed that α″ martensitic transformation and nano-twinning plus ß-to-α phase transformation with α″ martensite as an intermediate phase occurred, in addition to substantial fine grains. The grain refinement mechanisms were mainly related to dynamic recovery dominated by dislocation migration alongside severe plastic deformation.

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PURPOSE: This work aims to unravel the intricacies of adiabatic rotating frame relaxometry in biological tissues. THEORY AND METHODS: The classical formalisms of dipolar relaxation R 1 ρ $$ {R}_{1\rho } $$ and R 2 ρ $$ {R}_{2\rho } $$ were systematically analyzed for water molecules reorienting on "fast" and "slow" timescales. These two timescales are, respectively, responsible for the absence and presence of R 1 ρ $$ {R}_{1\rho } $$ dispersion. A time-averaged R 1 ρ $$ {R}_{1\rho } $$ or R 2 ρ $$ {R}_{2\rho } $$ over an adiabatic pulse duration was recast into a sum of R 1 $$ {R}_1 $$ and R 2 $$ {R}_2 $$ , but with different weightings. These weightings depend on the specific modulations of adiabatic pulse waveforms. In this context, stretched hyperbolic secant ( HSn $$ HSn $$ ) pulses were characterized. Previously published H S 1 $$ HS1 $$ R 1 ρ $$ {R}_{1\rho } $$ , continuous-wave (CW) R 1 ρ $$ {R}_{1\rho } $$ , and R 1 $$ {R}_1 $$ measures from 12 agarose phantoms were used to validate the theoretical predictions. A similar validation was also performed on previously published HSn $$ HSn $$ R 1 ρ $$ {R}_{1\rho } $$ ( n $$ n $$ =1, 4, 8) and HS 1 $$ HS1 $$ R 2 ρ $$ {R}_{2\rho } $$ from bovine cartilage specimens. RESULTS: Longitudinal relaxation weighting decreases for HSn $$ HSn $$ pulses as n $$ n $$ increases. Predicted CW R 1 ρ cal $$ {R}_{1\rho}^{cal} $$ values from agarose phantoms align well with the measured CW R 1 ρ exp $$ {R}_{1\rho}^{exp} $$ values, as indicated by a linear regression function: R 1 ρ cal = 1.04 * R 1 ρ exp - 1.96 $$ {R}_{1\rho}^{cal}={1.04}^{\ast }{R}_{1\rho}^{exp}-1.96 $$ . The predicted adiabatic R 1 ρ $$ {R}_{1\rho } $$ and R 2 ρ $$ {R}_{2\rho } $$ from cartilage specimens are consistent with those previously measured, as quantified by: R 1 ρ , 2 ρ cal = 1.10 * R 1 ρ , 2 ρ exp - 0.41 $$ {R}_{1\rho, 2\rho}^{cal}={1.10}^{\ast }{R}_{1\rho, 2\rho}^{exp}-0.41 $$ . CONCLUSION: This work has theoretically and experimentally demonstrated that adiabatic R 1 ρ $$ {R}_{1\rho } $$ and R 2 ρ $$ {R}_{2\rho } $$ can be recast into a sum of R 1 $$ {R}_1 $$ and R 2 $$ {R}_2 $$ , with varying weightings. Therefore, any suggestions that adiabatic rotating frame relaxometry in biological tissues could provide more information than the standard R 1 $$ {R}_1 $$ and R 2 $$ {R}_2 $$ warrant closer scrutiny.

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Small metal-rich semiconducting quantum dots (QDs) are promising for solid-state lighting and single-photon emission due to their highly tunable yet narrow emission line widths. Nonetheless, the anionic ligands commonly employed to passivate these QDs exert a substantial influence on the optoelectronic characteristics, primarily owing to strong electron-phonon interactions. In this work, we combine time-domain density functional theory and nonadiabatic molecular dynamics to investigate the excited charge carrier dynamics of Cd28Se17X22 QDs (X = HCOO-, OH-, Cl-, and SH-) at ambient conditions. These chemically distinct but regularly used molecular groups influence the dynamic surface-ligand interfacial interactions in Cd-rich QDs, drastically modifying their vibrational characteristics. The strong electron-phonon coupling leads to substantial transient variations at the band edge states. The strength of these interactions closely depends on the physicochemical characteristics of passivating ligands. Consequently, the ligands largely control the nonradiative recombination rates and emission characteristics in these QDs. Our simulations indicate that Cd28Se17(OH)22 has the fastest nonradiative recombination rate due to the strongest electron-phonon interactions. Conversely, QDs passivated with thiolate or chloride exhibit considerably longer carrier lifetimes and suppressed nonradiative processes. The ligand-controlled electron-phonon interactions further give rise to the broadest and narrowest intrinsic optical line widths for OH and Cl-passivated single QDs, respectively. Obtained computational insights lay the groundwork for designing appropriate passivating ligands on metal-rich QDs, making them suitable for a wide range of applications, from blue LEDs to quantum emitters.

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The training of neural networks (NNs) is a computationally intensive task requiring significant time and resources. This article presents a novel approach to NN training using adiabatic quantum computing (AQC), a paradigm that leverages the principles of adiabatic evolution to solve optimization problems. We propose a universal AQC method that can be implemented on gate quantum computers, allowing for a broad range of Hamiltonians and thus enabling the training of expressive neural networks. We apply this approach to various neural networks with continuous, discrete, and binary weights. The study results indicate that AQC can very efficiently evaluate the global minimum of the loss function, offering a promising alternative to classical training methods.

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Titanium parts fabricated by additive manufacturing, i.e., laser or electron beam-powder bed fusion (L- or EB-PBF), usually exhibit columnar grain structures along the build direction, resulting in both microstructural and mechanical anisotropy. Post-heat treatments are usually used to reduce or eliminate such anisotropy. In this work, Ti-6Al-2Zr-1Mo-1V (TA15) alloy samples were fabricated by L-PBF to investigate the effect of post-heat treatment and load direction on the dynamic response of the samples. Post-heat treatments included single-step annealing at 800 °C (HT) and a hot isotropic press (HIP). The as-built and heat-treated samples were dynamically compressed using a split Hopkinson pressure bar at a strain rate of 3000 s-1 along the horizontal and vertical directions paralleled to the load direction. The microstructural observation revealed that the as-built TA15 sample exhibited columnar grains with fine martensite inside. The HT sample exhibited a fine lamellar structure, whereas the HIP sample exhibited a coarse lamellar structure. The dynamic compression results showed that post-heat treatment at 800 °C led to reduced flow stress but enhanced uniform plastic strain and damage absorption work. However, the HIP samples exhibited both higher stress, uniform plastic strain, and damage absorption work owing to the microstructure coarsening. Additionally, the load direction had a subtle influence on the flow stress, indicating the negligible anisotropy of flow stress in the samples. However, there was more significant anisotropy of the uniform plastic strain and damage absorption. The samples had a higher load-bearing capacity when dynamically compressed perpendicular to the build direction.

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Adiabatic demagnetization refrigeration is known to be the only cryogenic refrigeration technology that can achieve ultralow temperatures (≪1 K) at gravity-free conditions. The key indexes to evaluate the performance of magnetic refrigerants are their magnetic entropy changes (-ΔSm) and magnetic ordering temperature (T0). Although, based on the factors affecting the -ΔSm of magnetic refrigerants, one has been able to judge if a magnetic refrigerant has a large -ΔSm, how to accurately predict their T0 remains a huge challenge due to the fact that the T0 of magnetic refrigerants is related to not only magnetic exchange but also single-ion anisotropy and magnetic dipole interaction. Here, we, taking GdCO3F (1), Gd(HCOO)F2, Gd2(SO4)3·8H2O, GdF3, Gd(HCOO)3 and Gd(OH)3 as examples, demonstrate that the T0 of magnetic refrigerants with very weak magnetic interactions and small anisotropy can be accurately predicted by integrating mean-field approximation with quantum Monte Carlo simulations, providing an effective method for predicting the T0 of ultralow-temperature magnetic refrigerants. Thus, the present work lays a solid foundation for the rational design and preparation of ultralow-temperature magnetic refrigerants in the future.

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In this article, we explore the construction of Hamiltonians with long-range interactions and their corrections using the short-range behavior of the wave function. A key aspect of our investigation is the examination of the one-particle potential, kept constant in our previous work, and the effects of its optimization on the adiabatic connection. Our methodology involves the use of a parameter-dependent potential dependent on a single parameter to facilitate practical computations. We analyze the energy errors and densities in a two-electron system (harmonium) under various conditions, employing different confinement potentials and interaction parameters. The study reveals that while the mean-field potential improves the expectation value of the physical Hamiltonian, it does not necessarily improve the energy of the system within the bounds of chemical accuracy. We also delve into the impact of density variations in adiabatic connections, challenging the common assumption that a mean field improves results. Our findings indicate that as long as energy errors remain within chemical accuracy, the mean field does not significantly outperform a bare potential. This observation is attributed to the effectiveness of corrections based on the short-range behavior of the wave function, a universal characteristic that diminishes the distinction between using a mean field or not.

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Furan-containing compounds distribute widely in food, herbal medicines, industrial synthetic products, and environmental media. These compounds can undergo oxidative metabolism catalyzed by cytochrome P450 enzymes (CYP450) within organisms, which may produce reactive products, possibly reacting with biomolecules to induce toxic effects. In this work, we performed DFT calculations to investigate the CYP450-mediated metabolic mechanism of furan-ring oxidation using 2-methylfuran as a model substrate, meanwhile, we studied the regioselective competition of another hydroxylation reaction involving methyl group of 2-methylfuran. As a result, we found the toxicological-relevant cis-enedione product can be produced from O-addition directly via a concerted manner without formation of an epoxide intermediate as traditionally believed. Moreover, our calculations demonstrate the kinetic and thermodynamic feasibility of both furan-ring oxidation and methyl hydroxylation pathways, although the former pathway is a bit more favorable. We then constructed a linear model to predict the rate-limiting activation energies (ΔE*) of O-addition with 11 diverse furan substates based on their adiabatic ionization potentials (AIPs) and condensation Fukui functions (CFFs). The results show a good predictive ability (R2=0.94, Q2CV=0.87). Therefore, AIP and CFF with clear physichem meanings relevant to the mechanism, emerge as pivotal molecular descriptors to enable the fast prediction of furan-ring oxidation reactivities for quick insight into the toxicological risk of furans, using just ground-state calculations.

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This paper investigates numerically the effect of damage evolution on adiabatic shear banding (ASB) formation and its transition to fracture during high-speed blanking of 304 stainless steel sheets. A structural-thermal-damage-coupled finite element (FE) analysis is developed in LS-DYNA considering the modified Johnson-Cook thermo-viscoplastic model for both plasticity flow rule and damage law, while further, a temperature-dependent fracture criterion is implemented by introducing a critical temperature. The modeling approach is initially validated against experimental data regarding the fracture profile and ASB width. Next, FE simulations are conducted to examine the effect of strain rate and temperature dependence on damage law, while the effect of damage coupling is also evaluated, aiming to highlight the connection between thermal and damage softening and attribute them a specific role regarding ASB formation and transition to fracture. Also, the influence of dynamic recrystallization (DRX) softening is studied macroscopically, while further, a parametric analysis of the Taylor-Quinney coefficient is conducted to highlight the effect of plastic work-to-internal heat conversion efficiency on ASB formation. The results revealed that the implementation of damage coupling reacts to reduced ASB width and provides an S-shaped fracture profile, while it also decreases the peak force and results in an earlier fracture. Both findings are enhanced when accounting further for DRX softening and a higher value of the Taylor-Quinney coefficient. Finally, the simulations indicated that thermal softening precedes damage softening, showing that the temperature rise is responsible for ASB initiation, while instead, damage evolution drives ASB propagation and fracture.

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Integrating hydrogen with CNG is crucial for carbon neutrality and environmental goals, as it enhances flame temperature, reduces emissions, and combats global warming. This study employs the CHEMKIN tool to examine combustion characteristics, including adiabatic flame temperature, mole fraction, normalization, and production rate, in H2-CNG mixtures under various atmospheric and operating conditions. Blending 50% hydrogen with CNG results in significant changes, including a temperature increase from 2322 to 2344 K when the hydrogen content is at 50%. The introduction of hydrogen causes a notable 30-35% reduction in CH4 mole fraction and a simultaneous 26.6% increase in C-normalized CH4 production. Free radicals play a role in affecting CO2 production, with the normalization of CO species increasing from 0.068 to 0.087. Through NSGA-II multi-objective optimization methods, the study identifies a 50% H2-50% CNG blend as the optimal choice for thermal and environmental performance. The study explores the energy and environmental impacts of incorporating hydrogen into CNG-air combustion, with a specific focus on the effects of 50% H2 blending with CNG. Hydrogen blending benefits from elevated adiabatic flame temperature and increased free radical formation, ultimately leading to emission reduction. These findings firmly establish H2-CNG mixtures as promising environmentally friendly alternatives with superior combustion characteristics. Their potential paves the way for significant progress towards achieving carbon neutrality and combating climate change through cleaner, more efficient fuel options.

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A physical platform for nodes of the envisioned quantum Internet is long-sought. Here we propose such a platform, along with a conceptually simple and experimentally uncomplicated quantum information processing scheme, realized in a system of multiple crystal-phase quantum dots. We introduce novel location qubits, describe a method to construct a universal set of all-optical quantum gates, and simulate their performance in realistic structures, including decoherence sources. Our results show that location qubits are robust against the main decoherence mechanisms, and realistic single-qubit gate fidelities exceed 99.9%. Our scheme paves a clear way toward constructing multiqubit solid-state quantum registers with a built-in photonic interface─a key building block of the forthcoming quantum Internet.

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Herein, we investigate the effects of the irreversible action of the medium on the theoretical elucidation of the IR spectrum of weakly H-bonded systems, a prototypical model which provides a rigorous treatment of the relaxation mechanisms impacts on the IR spectral density. The attention will be focused particularly on the effect of indirect damping on the IRυS(X-H⃗) spectrum beyond the harmonic and adiabatic approximations. The ultimate objective of the present investigation is the treatment of the action of the surrounding of the intermonomer modes of H-bonded systems, which must induce a broadening of the Dirac delta peaks, the nature of which, as shown by Maréchal and Witkowski theory, is a Franck-Condon progression. The quantum treatment of the IR absorption band reveals that quantum relaxation of the intermonomer mode of H-bonded complexes could be successfully approached by a non-Hermitian Hamiltonian formalism. Motivated by development of a second method that will be able to validate the first approach, a computationally efficient algorithm was proposed for elucidating the quantum indirect relaxation using Hermitean Hamiltonians. The real eigenvalues, corresponding to different energies of the system are considered to be complex by adjunction of the imaginary parts, which reflects the action of the indirect irreversible action of the medium. These two crude approaches may pave the way for the incorporation of the mechanism of indirect relaxation in more physical and complex situations dealing, particularly, with tunnelling effects in strong H-bonded species, Fermi resonances, and Davydov coupling for cyclic H-bonds dimers beyond the harmonic and adiabatic assumptions.

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Experiments have demonstrated that mild humidity can enhance the stability of the CsPbBr3 perovskite, though the underlying mechanism remains unclear. Utilizing ab initio molecular dynamics, ring polymer molecular dynamics, and non-adiabatic molecular dynamics, our study reveals that nuclear quantum effects (NQEs) play a crucial role in stabilizing the lattice rigidity of the perovskite while simultaneously shortening the charge carrier lifetime. NQEs reduce the extent of geometric disorder and the number of atomic fluctuations, diminish the extent of hole localization, and thereby improve the electron-hole overlap and non-adiabatic coupling. Concurrently, these effects significantly suppress phonon modes and slow decoherence. As a result, these factors collectively accelerate charge recombination by a factor of 1.42 compared to that in scenarios excluding NQEs. The resulting sub-10 ns recombination time scales align remarkably well with experimental findings. This research offers novel insight into how moisture resistance impacts the stability and charge carrier lifetime in all-inorganic perovskites.

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Continuous tuning of the frequency of laser light serves as the fundamental basis for a myriad of applications spanning basic scientific research to industrial settings. These applications encompass endeavors such as the detection of gravitational waves, the development of precise optical clocks, environmental monitoring for health and ecological purposes, as well as distance measurement techniques. However, achieving a broad tuning range exceeding 100 GHz along with sub-microsecond tuning times, inherent linearity in tuning, and coherence lengths beyond 10 m presents significant challenges. Here, we demonstrate that electro-optically driven adiabatic frequency converters utilizing high-Q microresonators fabricated from lithium niobate possess the capability to convert arbitrary voltage signals into frequency chirps with temporal resolutions below 1 µs. The temporal evolution of the frequency correlates accurately with the applied voltage signal. We have achieved to generate 200-ns-long frequency chirps with deviations of less than 1 % from perfect linearity without requiring supplementary measures. The coefficient of determination is R 2 > 0.999 . Moreover, the coherence length of the emitted light exceeds 20 m. To validate these findings, we employ the linear frequency sweeps for Frequency-Modulated Continuous Wave (FMCW) LiDAR covering distances ranging from 0.5 to 10 m. Leveraging the demonstrated nanosecond-level tuning capabilities, coupled with the potential to tune the eigenfrequency of lithium-niobate-based resonators by several hundred GHz, our results show that electro-optically driven adiabatic frequency converters can be used in applications that require ultrafast and flexible continuous frequency tuning characterized by inherent linearity and substantial coherence length.

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PURPOSE: The purpose of this study is to improve the image quality of diffusion-weighted images obtained with a single RF transmit channel 7 T MRI setup using time-resampled frequency-offset corrected inversion (TR-FOCI) pulses to refocus the spins in a twice-refocused spin-echo readout scheme. METHODS: We replaced the conventional Shinnar-Le Roux-pulses in the twice refocused diffusion sequence with TR-FOCI pulses. The slice profiles were evaluated in simulation and experimentally in phantoms. The image quality was evaluated in vivo comparing the Shinnar-Le Roux and TR-FOCI implementation using a b value of 0 and of 1000 s/mm2. RESULTS: The b0 and diffusion-weighted images acquired using the modified sequence improved the image quality across the whole brain. A region of interest-based analysis showed an SNR increase of 113% and 66% for the nondiffusion-weighted (b0) and the diffusion-weighted (b = 1000 s/mm2) images in the temporal lobes, respectively. Investigation of all slices showed that the adiabatic pulses mitigated B 1 + $$ {B}_1^{+} $$ inhomogeneity globally using a conventional single-channel transmission setup. CONCLUSION: The TR-FOCI pulse can be used in a twice-refocused spin-echo diffusion pulse sequence to mitigate the impact of B 1 + $$ {B}_1^{+} $$ inhomogeneity on the signal intensity across the brain at 7 T. However, further work is needed to address SAR limitations.

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Background: Myelin water imaging (MWI) is a myelin-specific technique, which has great potential for the assessment of demyelination and remyelination. This study develops a new MWI method, which employs a short repetition time adiabatic inversion recovery (STAIR) technique in combination with a commonly used fast spin echo (FSE) sequence and provides quantification of myelin water (MW) fractions. Method: Whole-brain MWI was performed using the short repetition time adiabatic inversion recovery prepared-fast spin echo (STAIR-FSE) technique on eight healthy volunteers (mean age: 38±14 years, four-males) and seven patients with multiple sclerosis (MS) (mean age: 53.7±8.7 years, two-males) on a 3T clinical magnetic resonance imaging scanner. To facilitate the quantification of apparent myelin water fraction (aMWF), a proton density-weighted FSE was also used during the scans to allow total water imaging. The aMWF measurements of MS lesions and normal-appearing white matter (NAWM) regions in MS patients were compared with those measured in normal white matter (NWM) regions in healthy volunteers. Both the analysis of variance (ANOVA) test and paired comparison were performed for the comparison. Results: The MW in the whole-brain was selectively imaged and quantified using the STAIR-FSE technique in all participants. MS lesions showed much lower signal intensities than NAWM in the STAIR-FSE images. ANOVA analysis revealed a significant difference in the aMWF measurements between the three groups. Moreover, the aMWF measurements in MS lesions were significantly lower than those in both NWM of healthy volunteers and NAWM of MS patients. Lower aMWF measurements in NAWM were also found in comparison with those in NWM. Conclusions: The STAIR-FSE technique is capable of measuring aMWF values for the indirect detection of myelin loss in MS, thus facilitating clinical translation of whole brain MWI and quantification, which show great potential for the detection and evaluation of changes in myelin in the brain of patients with MS for future larger cohort studies.

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We present a first spectroscopic characterization of the homoatomic polyhalogen tetrabromine, Br4, in the gas phase. Photolysis of CHBr3 at 248 nm is used to generate atomic bromine radicals in a flow tube reactor. Resulting combination products are detected by photoionization mass spectrometry at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Interpretation of the experimental mass spectra is informed by calculated adiabatic ionization energies carried out at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ//cam-B3LYP/6-311++g** levels of theory. Tunable VUV synchrotron radiation enables the collection of the mass-selected photoionization spectra by which Br4 is assigned using Franck-Condon simulations of a Br2 dimer with a stretched tetrahedral geometry.

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Chlorinated organic compounds are prominently used for industrial production, but their vapors and emission byproducts can cause detrimental effects to human health and the environment. To accurately quantify organochlorine compounds, the absolute photoionization cross section of tetrachloroethylene, chlorobenzene, 1,2-dichlorobenzene, and chloroacetone are measured using multiplexed synchrotron photoionization mass spectrometry at the Advanced Light Source at Lawrence Berkeley National Laboratory. These measurements allow for the estimation of the C-Cl photoionization cross section, increasing quantification accuracy of chlorinated emissions for kinetic modeling and pollutant mitigation. CBS-QB3 calculations of adiabatic ionization energies and thermochemical appearance energies are also presented and agree well with the experimental results.

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The absolute photoionization cross section of the monoterpenoid, alpha-pinene (AP), is presented together with the relative photoionization cross sections of its dissociative fragments for the first time. Experiments are performed via multiplexed vacuum ultraviolet (VUV) synchrotron photoionization (PI) mass spectrometry in the 8.0-11.0 eV energy range. Experimental work is conducted at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Dissociative fragments were identified at m/z 121, 94, 93, 92, and 80. The photoionization cross section for the parent mass at 11.0 eV was determined to be 17±4 Mb with a total ionization cross section of 92±23 Mb at the same photon energy. Experimental appearance energies of dissociative ionization fragments and potential dissociative ionization pathways calculated at the G4 level of theory are presented as well.