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(top left) The electron density pictures for the movie stripwere adapted from Figure 2 in Bruner, A.; Hernandez, S.; Mauger, F.; Abanador,P. M.; LaMaster, D. J.; Gaarde, M. B.; Schafer, K.
Archmodels vol. 123 includes 36 highly detailed 3d models of bedroom sets. All models are ready to use in your visualizations. Scene is not included. Archmodels volume 103 gives you 80 professional, highly detailed objects for architectural visualizations. This dvd comes with mid poly models of night skyscrapers with all textures and materials. It is ready to use, just put it into your scene. Why waste costly time for making something that you can have from the best at Evermotion?
J.; Lopata, K. AttosecondCharge Migration with TDDFT: Accurate Dynamics from a Well-Defined InitialState. 2017, 8, 3991–3996. (middle)The electron momentum distribution picture was adapted from Figure 1 in Winney,A. H.; Basnayake, G.; Debrah, D.
K.; Hoerner, P.; Liao,Q.; Schlegel, H. Disentangling Strong-Field Multielectron Dynamics withAngular Streaking. 2018, 9, 2539–2545. (lower right) From the TOC in Xu, H.; Okino, T.; Kudou,T.; Yamanouchi, K.; Roither, S.; Kitzler, M.; Baltuska, A.; Chin, S.-L. Effectof Laser Parameters on Ultrafast Hydrogen Migration in Methanol Studied byCoincidence Momentum Imaging, J. A 2012, 116, 2686–2690. The kinetics of the reaction of the simplest Criegee intermediate CH2OO with CH3SH was measured with transient IR absorption spectroscopy in a temperature-controlled flow reaction cell, and the bimolecular rate coefficients were measured from 278 to 349 K and at total pressure from 10 to 300 Torr.
The measured bimolecular rate coefficient at 298 K and 300 Torr is (1.01 ± 0.17) × 10–12 cm3 s–1. The results exhibit a weak negative temperature dependence: the activation energy Ea (k = Ae–Ea/RT) is −1.83 ± 0.05 kcal mol–1, measured at 30 and 100 Torr. Quantum chemistry calculations of the reaction rate coefficient at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level (1.6 × 10–12 cm3 s–1 at 298 K; Ea = – 2.80 kcal mol–1) are in reasonable agreement with the experimental results. The experimental and theoretical results of the reaction of CH2OO with CH3SH are compared to the reactions of CH2OO with methanol and hydrogen sulfide, and the trends in reactivity are discussed. The results of the present work indicate that this reaction has a negligible influence to atmospheric CH2OO or CH3SH. The crossed beams reactions of the 1-propynyl radical (CH3CC; X2A1) with 1,3-butadiene (CH2CHCHCH2; X1Ag), 1,3-butadiene-d6 (CD2CDCDCD2; X1Ag), 1,3-butadiene-d4 (CD2CHCHCD2; X1Ag), and 1,3-butadiene-d2 (CH2CDCDCH2; X1Ag) were performed under single collision conditions at collision energies of about 40 kJ mol–1. The underlying reaction mechanisms were unraveled through the combination of the experimental data with electronic structure calculations at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) + ZPE(B3LYP/6-311G(d,p) level of theory along with statistical Rice–Ramsperger–Kassel–Marcus (RRKM) calculations.
Together, these data suggest the formation of the thermodynamically most stable C7H8 isomer—toluene (C6H5CH3)—via the barrierless addition of 1-propynyl to the 1,3-butadiene terminal carbon atom, forming a low-lying C7H9 intermediate that undergoes multiple isomerization steps resulting in cyclization and ultimately aromatization following hydrogen atom elimination. RRKM calculations predict that the thermodynamically less stable isomers 1,3-heptadien-5-yne, 5-methylene-1,3-cyclohexadiene, and 3-methylene-1-hexen-4-yne are also synthesized. Since the 1-propynyl radical may be present in cold molecular clouds such as TMC-1, this pathway could potentially serve as a carrier of the methyl group incorporating itself into methyl-substituted (poly)acetylenes or aromatic systems such as toluene via overall exoergic reaction mechanisms that are uninhibited by an entrance barrier. Such pathways are a necessary alternative to existing high energy reactions leading to toluene that are formally closed in the cold regions of space and are an important step toward understanding the synthesis of polycyclic aromatic hydrocarbons (PAHs) in space’s harsh extremes.
Phase modulation and phase cycling schemes have been commonly used in electronic two-dimensional (2D) spectroscopy where the observables are incoherent signals such as fluorescence or photocurrent. Although the methods have distinct advantages compared to the coherent signal-detected 2D spectroscopy in sensitivity, possibility to measure spectra from isolated quantum systems and direct visualization of the contributions from the different states to the action signals, and ambiguities in interpreting the spectra have emerged. Recent reports have shown that apart from the nonlinear signals from the four pulse interactions, mixing of the linear signals due to nonlinear population dynamics during the long measurement time of the action signals can also contribute to the measured 2D spectra. Exciton–exciton annihilation has been considered to play a major role in the mixing of the linear signals. Thus, it has become important to further characterize the origin of the measured signals. Here, using a nonperturbative simulation of the 2D spectra based on the time evolution of the density matrix in the Lindblad form, we show that the exciton–exciton annihilation contributes to the measured signal only if the quantum yields of the different excited states are not the same.
In these cases, the mixed signals can be distinguished from the true nonlinear signals if the phases are measured with respect to the linear signals. In action-detected 2D spectra, the mixed signals have a π phase shift relative to the true nonlinear signals. A detailed discussion on the experimental implementations of the schemes used in the simulations is also provided. We propose a set of chemical reaction mechanisms of unidirectional proton transfers, which may possibly work as an elementary process in chemical and biological systems. Being theoretically derived based on our series of studies on charge separation dynamics in water splitting by Mn oxides, the present mechanisms have been constructed after careful exploration over the accumulated biological studies on cytochrome c oxidase (CcO) and bacteriorhodopsin.
In particular, we have focused on the biochemical findings in the literature that unidirectional transfers of approximately two protons are driven by one electron passage through the reaction center (binuclear center) in CcO, whereas no such dissipative electron transfer is believed to be demanded in the proton transport in bacteriorhodopsin. The proposed basic mechanisms of unidirectional proton transfers are further reduced to two elementary dynamical processes, namely, what we call the coupled proton and electron-wavepacket transfer (CPEWT) and the inverse CPEWT. To show that the proposed mechanisms can indeed be materialized in a molecular level, we construct model systems with possible molecules that are rather familiar in biological chemistry, for which we perform the ab initio calculations of full-dimensional nonadiabatic electron-wavepacket dynamics coupled with all nuclear motions including proton transfers.
Spectroscopy, Molecular Structure, and Quantum Chemistry. Quantifying the effect of anharmonicity on the infrared spectrum of large molecules such as polycyclic aromatic hydrocarbons (PAHs) at high temperatures is the focus of a number of theoretical and experimental studies, many of them motivated by astrophysical applications.
We recorded the IR spectrum of pyrene C16H10 microcrystals embedded in KBr pellets over a wide range of temperatures (14–723 K) and studied the evolution of band positions, widths, and integrated intensities with temperature. We identified jumps for some of the spectral characteristics of some bands in the 423–473 K range.
These were attributed to a change of phase from crystal to molten in condensed pyrene, which appears to affect more strongly bands involving large CH motions. Empirical anharmonicity factors that quantify the linear evolution of band positions and widths with temperature for values larger than ∼150–250 K, depending on the band, were retrieved from both phases and averaged to provide recommended values for these anharmonicity factors. The derived values were found to be consistent with available gas phase data. We conclude about the relevance of the methodology to produce data that can be compared with calculated anharmonic IR spectra and provide input for models that simulate the IR emission of astro-PAHs. We report the fingerprint IR spectra of mass-isolated gaseous coordination complexes of 2,2′-bipyridine (bpy) and 1,4,8,11-tetra-azacyclotetradecane (cyclam) with a copper ion in its I and II oxidation states. Experiments are carried out in a quadrupole ion trap (QIT) mass spectrometer coupled to the FELIX infrared free-electron laser.
Dications are prepared using electrospray ionization (ESI), while monocations are generated by charge reduction of the dication using electron transfer-reduction (ETR) in the QIT. Interestingly, Cu(bpy)2+ can also be generated directly using ESI, so that its geometries as produced from ETR and ESI can be compared. The effects of charge reduction on the IR spectra are investigated by comparing the experimental spectra with the IR spectra modeled by density functional theory. Reduction of Cu(II) to the closed-shell Cu(I) ion retains the square-planar geometry of the Cu–cyclam complex. In contrast, for the bis–bpy complex with Cu, charge reduction induces a conversion from a near-square-planar to a tetrahedral geometry.
The geometry of Cu(bpy)2+ is identical to that of the complex generated directly from ESI as a native structure, which indicates that the ETR product ion thermalizes. For Cu(cyclam)+, however, the square-planar geometry of the 2+ complex is retained upon charge reduction, although a (distorted) tetrahedral geometry was predicted to be lower in energy. These differences are attributed to different barriers to rearrangement. Photoelectron spectroscopy of the biacetyl (dimethylglyoxal) anion reveals the properties of the ground singlet and lowest triplet electronic states of the neutral biacetyl (BA) molecule. Due to the broad and congested nature of the singlet transition, which peaks at a vertical detachment energy VDE = 1.12(5) eV, only an upper bound of the adiabatic electron affinity of BA could be determined: EA(BA).
The ν3 antisymmetric stretching mode of disilicon-carbide, Si2C, was studied using a narrow line width infrared quantum cascade laser spectrometer operating at 8.3 μm. The Si2C molecules were produced in an Nd:YAG laser ablation source from a pure silicon sample with the addition of a few percent methane diluted in a helium buffer gas. Subsequent adiabatic expansion was used to cool the gas down to rotational temperatures of a few tens of kelvin.
A total of 183 infrared transitions recorded in the spectral range between 1200 and 1220 cm–1 were assigned to the fundamental ν3 mode of Si2C. In addition, pure rotational transitions of Ka = 1 and 2 between 278 and 375 GHz were recorded using a supersonic jet spectrometer for submillimeter wavelengths. Molecular parameters for the (v1v2v3) = (001) vibrationally excited state were derived and improved molecular parameters for the vibrational ground-state (000) were obtained from a global fit data analysis, which includes our new laboratory data and millimeter wavelength data from the literature. We found the rotational levels Ka = 0 and Ka = 2 in the vibrationally excited (001) state being perturbed by a Coriolis-type interaction with energetically close lying levels of the symmetric stretching and triple-excited bending mode (130). The data analysis was supported by quantum chemical calculations performed at the coupled-cluster level of theory. All experimental results were found to be in excellent agreement with the theory.
Aminoisobutyric acid (Aib) oligomers are known to form racemic mixtures of enantiomeric left- and right-handed structures. The introduction of a chiral cap converts the enantiomeric structures into diastereomers that, in principle, afford spectroscopic differentiation. Here, we screen different C-terminal caps based on a model Aib dipeptide using double resonance laser spectroscopy in the gas phase to record IR and UV spectra of individual conformations present in the supersonic expansion: NH-benzyl (NHBn) as a reference structure because of its common use as a fluorophore in similar studies, NH-p-fluorobenzyl (NHBn-F), and α-methylbenzylamine (AMBA). For both the NHBn and NHBn-F caps, a single conformer is observed, with infrared spectra assignable to an enantiomeric pair of type II/II′ β-turns in these molecules lacking a chiral center. The higher oscillator strength of the NHBn-F cap enabled UV–UV hole burning, not readily accomplished with the NHBn cap. The AMBA-capped structure, with its chiral center, produced two unique conformers, one of which was a nearly identical left-handed type II β-turn, while the minor conformer is assigned to a C7–C7 sequential double ring, which is an emergent form of a 27-ribbon.
Although not observed, the type II′ β-turn diastereomer, with opposite handedness, is calculated to be 11 kJ/mol higher in energy, a surprisingly large difference. This destabilization is attributed primarily to steric interference between the C-terminal acyl oxygen of the peptide and the chirality-inducing methyl of the AMBA group. Last, computational evidence indicates that the use of an N-terminal aromatic cap hinders the formation of a 310-helix in Ac-Aib2 dipeptides. As a result of continuing ionic liquid research, it becomes clearer that charge transfer in ionic liquids has a physical reality.
In a recent publication, we demonstrated the utility of simple density functional theory descriptors to estimate charge transfer for a large number of ion combinations, which is possible because the ions are treated separately. A major disadvantage found was that the charge transfer was systematically overestimated. In this work, we introduce a correction to account for the losses in Coulomb attraction when charge is transferred from the anion to the cation. We find that accounting for these losses is important to describe charge transfer in ionic liquids appropriately. The advantage that the calculations can be performed separately on the individual, isolated ions is maintained.
The corrected as well as the uncorrected charge transfer have been calculated for over 4000 cation–anion combinations at the R(O)B3LYP/6-311+G(2d,p)//RB3LYP/6-31+G(d,p) level of theory. With the correction, the absolute values for the charge transfer are no longer unrealistically high and agree well with other charge transfer estimates from the literature. In general, the cumulative nature of the Haven ratio is now correctly mirrored in the relationship between the corrected theoretical charge transfer and the experimental estimate from the Nernst–Einstein relation.
Earlier findings on the similarities between ether-functionalized and nonfunctionalized ionic liquids are confirmed. However, we also observe inconsistencies when using the experimental charge transfer estimates together with the ionicity interpretation of the Haven ratio. These can be interpreted as a hint toward the latter premise being wrong. Many-body potentials up to fourth order are constructed using nonrelativistic, scalar-relativistic, and relativistic coupled-cluster theory to accurately describe the interaction between superheavy oganesson atoms. The obtained distance-dependent energy values were fitted to extended two-body Lennard-Jones and three-body Axilrod–Teller–Muto potentials, with the fourth-order term treated through a classical long-range Drude dipole interaction model. From these interaction potentials, spectroscopic constants for the oganesson dimer and solid-state properties were obtained. Furthermore, these high-level results are compared to scalar-relativistic and two-component plane-wave DFT calculations based on a tailor-made projector augmented wave pseudopotential (PAW-PP) and newly derived parameters for Grimme’s dispersion correction.
It is shown that the functionals PBE-D3(BJ), PBEsol, and in particular SCAN provide excellent agreement with the many-body reference for solid oganesson. Finally, the results for oganesson are compared and related to the lighter rare gas elements, and periodic trends are discussed. The best currently available set of temperature-dependent nonrigid rotor anharmonic oscillator (NRRAO) thermochemical and thermophysical properties of hydroxymethyl radical is presented. The underlying partition function relies on a critically evaluated complement of accurate experimental and theoretical data and is constructed using a two-pronged strategy that combines contributions from large amplitude motions obtained from direct counts, with contributions from the other internal modes of motion obtained from analytic NRRAO expressions. The contributions from the two strongly coupled large-amplitude motions of CH2OH, OH torsion and CH2 wag, are based on energy levels obtained by solving the appropriate two-dimensional projection of a fully dimensional potential energy surface that was recently obtained at the CCSD(T)/cc-pVTZ level of theory. The contributions of the remaining seven, more rigid, vibrational modes and of the external rotations are captured by NRRAO corrections to the standard rigid rotor harmonic oscillator (RRHO) treatment, which include corrections for vibrational anharmonicities, rotation-vibration interaction, Coriolis effects, and low temperature.
The basic spectroscopic constants needed for the construction of the initial RRHO partition function rely on experimental ground-state rotational constants and the best available experimental fundamentals, additionally complemented by fundamentals obtained from the variational solution of the full-dimensional potential energy surface using a recently developed two-component multilayer Lanczos algorithm. The higher-order spectroscopic constants necessary for the NRRAO corrections are extracted from a second-order variational perturbation treatment (VPT2) of the same potential energy surface.
The Lanczos solutions of the fully dimensional surface are validated against available experimental data, and the VPT2 results and the solutions of the reduced dimensionality surface are validated both against the Lanczos solutions and available experiments. The NRRAO thermophysical and thermochemical properties, given both in tabular form and as seven- and nine-coefficient NASA polynomials, are compared to previous results.
The absorption spectra of acetylene (HCCH) and vinylidene (H2CC) as well as their deuterated isotopologues are investigated theoretically on a near spectroscopically accurate full-dimensional potential energy surface reported in an earlier publication, using dipole moment surfaces reported in this work, which are constructed with a neural network method from a large number of ab initio data points. These global surfaces cover not only the deep acetylene well but also the vinylidene well, as well as the transition region between the two isomers. The agreement with available experimental data for acetylene is excellent, validating both the potential energy surface and the dipole moment surfaces. The infrared spectra of vinylidene and its deuterated isotopologues are predicted. The potential and dipole moment surfaces lay the foundation for future spectroscopic studies of the acetylene–vinylidene isomerization involving large-amplitude motions. Environmental, Combustion, and Atmospheric Chemistry; Aerosol Processes, Geochemistry, and Astrochemistry.
A precise and complete thermodynamic, Raman spectroscopic, and ultraviolet–visible (UV–vis) optical characterization of the deltic, squaric, and croconic cyclic oxocarbon acids is obtained using theoretical solid-state methods employing very demanding calculation parameters. The computed fundamental thermodynamic properties include the isobaric specific heat, the entropy, the enthalpy, and the Gibbs free energy as a function of temperature. The calculated specific heats at 298.15 K of the deltic, squaric, and croconic acids are 89.7, 111.2, and 133.2 J mol–1 K–1, respectively, and the corresponding entropies are 98.3, 117.3, and 136.5 J mol–1 K–1. The only value of these properties known from experimental measurements is the specific heat of the squaric acid, which differs from the computed value at 315 K by about 4.9%. The calculated values of the thermodynamic properties are then used to determine the thermodynamic properties of formation of these materials in terms of the elements. As an application of the calculated thermodynamic properties of formation, the Gibbs free energies of reaction and associated reaction constants are evaluated for the reactions of thermal decomposition and complete combustion of the squaric and croconic acids and the reaction of interconversion between them. The only available experimental values of these properties, namely, the enthalpies of combustion of squaric and croconic acids at room temperature, are reproduced theoretically with high accuracy.
The Raman spectra of these materials are also computed using density functional perturbation theory. The analysis of the theoretical Raman spectra of these materials points out to significant differences with respect to their usual empirical assignment.
Therefore, the Raman spectra of these materials are fully reassigned. Finally, the ultraviolet–visible (UV–vis) optical properties of the deltic, squaric, and croconic acids are computed. The UV–vis absorption spectrum of the croconic acid in the spectral region 225–425 nm and the UV absorption spectrum of the squaric acid in the region 200–350 nm, which had previously been measured experimentally, are well reproduced. The corresponding spectrum for the deltic acid and the reflectivity, optical conductivity, dielectric, refractive index, and loss optical functions of the three materials, which had never been published as far as we know, are reported as a function of the wavelength of incident radiation in the range 200–750 nm. The origin of the peaks in the absorption spectra, which had not been analyzed so far, is unveiled here by examining the interband electronic transitions in these materials. The newly developed method of fragility spectra for observation of bond breaking and formation upon a reaction has been applied to the canonical reaction series of the double proton transfer (DPT).
Formic acid and its thio-analogues HCXYH (X, Y = O, S) have been chosen for the analysis. Very accurate linear correlations have been determined between the nondiagonal elements of the connectivity matrix, essential for the method, and the Wiberg bond orders for the corresponding bonds. Relation of the slope of this correlation to the global softness and to the atomic numbers of the bonded atoms has been proved, thus corroborating the c-DFT formula describing the fragility spectra. The electron density changes in bonds, as observed by the fragility spectra, are in harmony with the curvature diagrams reported by other authors. The accurate evaluation of the Wigner phase space density for multidimensional system remains a challenging task. Path integral Monte Carlo methods offer a numerically exact approach for obtaining the Boltzmann density in coordinate space, but the Fourier-type integral required to construct the Wigner distribution generally leads to poor convergence.
This paper describes a path integral method for constructing the Wigner density which substantially mitigates the Monte Carlo sign problem and thus is applicable to systems with many degrees of freedom. The starting point is the path integral representation of the coherent state density, which does not involve a Fourier integral and thus converges rapidly. We then use the relation between the coherent state and Wigner densities to construct the Wigner function, taking advantage of destructive phase cancellation to truncate the infinite series and thus confine the integrand, avoiding highly oscillatory regions. We also describe the use of information-guided noise reduction (IGNoR) to improve the Monte Carlo statistics in the most challenging regimes.
The method is applied to strongly anharmonic one-dimensional models, a system-bath Hamiltonian, as well as the formamide molecule within an ab initio quartic potential, and the results are compared to those obtained by various approximate methods. These calculations suggest that the coherent state-based path integral method described in this paper offers an efficient, numerically exact approach for constructing the Wigner phase space density in systems of many degrees of freedom, and thus will be useful for quantizing the initial condition in classical trajectory-based simulations of dynamical properties. Modern machine learning provides promising methods for accelerating the discovery and characterization of novel chemical species. However, in many areas experimental data remain costly and scarce, and computational models are unavailable for targeted figures of merit.
Here we report a promising pathway to address this challenge by using chemical latent space enrichment, whereby disparate data sources are combined in joint prediction tasks to enable improved prediction in data-scarce applications. The approach is demonstrated for pKa prediction of moderately sized molecular species using a combination of experimentally available pKa data and density functional theory-based characterizations of the (de)protonation free energy. A novel autoencoder framework is used to create a continuous chemical latent space that is then used in single and joint training tasks for property prediction. By combining these two data sets in a jointly trained autoencoder framework, we observe mutual improvement in property prediction tasks in the scarce data limit. We also demonstrate an enrichment mechanism that is unique to latent space training, whereby training on excess computational data can mitigate the prediction losses associated with scarce experimental data and advantageously organize the latent space. These results demonstrate that disparate chemical data sources can be advantageously combined in an autoencoder framework with potential general application to data-scarce chemical learning tasks. We redeveloped the ReaxFF force field parameters for Si/O/H interactions that enable molecular dynamics (MD) simulations of Si/SiO2 interfaces and O diffusion in bulk Si at high temperatures, in particular with respect to point defect stability and migration.
Our calculations show that the new force field framework (ReaxFFpresent), which was guided by the extensive quantum mechanical-based training set, describes correctly the underlying mechanism of the O-migration in Si network, namely, the diffusion of O in bulk Si occurs by jumping between the neighboring bond-centered sites along a path in the (110) plane, and during the jumping, O goes through the asymmetric transition state at a saddle point. Additionally, the ReaxFFpresent predicts the diffusion barrier of O-interstitial in the bulk Si of 64.8 kcal/mol, showing a good agreement with the experimental and density functional theory values in the literature. The new force field description was further applied to MD simulations addressing O diffusion in bulk Si at different target temperatures ranging between 800 and 2400 K. According to our results, O diffusion initiates at the temperatures over 1400 K, and the atom diffuses only between the bond-centered sites even at high temperatures. In addition, the diffusion coefficient of O in Si matrix as a function of temperature is in overall good agreement with experimental results.
As a further step of the force field validation, we also prepared amorphous SiO2 (a-SiO2) with a mass density of 2.21 gr/cm3, which excellently agrees with the experimental value of 2.20 gr/cm3, to model a-SiO2/Si system. After annealing the a-SiO2/Si system at high temperatures until below the computed melting point of bulk Si, the results show that ReaxFFpresent successfully reproduces the experimentally and theoretically defined diffusion mechanism in the system and succeeded in overcoming the diffusion problem observed with ReaxFFSiOH(2010), which results in O diffusion in the Si substrate even at the low temperature such as 300 K.
Evermotion – Archmodels vol 132 (3dmax – vray)Info:Archmodels vol. 132 includes 50 high quality 3d models for architectural visualizations. This collection comes with low poly cars models with all textures and materials. All vehicles are from our HDCars collections (ALL models from all 5 volumes), but in optimized, low-poly versions and without characteristic elements like for eg. Interior of every car is separated as a group – so can be easily removed.Presented models and scenes were rendered in V-ray with 3ds max.Scenes are not included.3dmax – vrayBuy here: navigation.