Molecular-level understanding of the rovibrational spectra of N2O in gaseous, supercritical, and liquid SF6and Xe

The transition between the gas-, supercritical-, and liquid-phase behavior is a fascinating topic, which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N2O embedded in xenon and SF6 as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics (MD) simulations together with accurate interaction potentials allows us to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch line shape for the stretch vibrations of N2O at low solvent densities to the Q-branch-like line shapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level

Low-temperature kinetics for the N + NO reaction: experiment guides the way

The reaction N(4S) + NO(X2Π) → O(3P) + N2(X1Σ+g) plays a pivotal role in the conversion of atomic to molecular nitrogen in dense interstellar clouds and in the atmosphere. Here we report a joint experimental and computational investigation of the N + NO reaction with the aim of providing improved constraints on its low temperature reactivity. Thermal rates were measured over the 50 to 296 K range in a continuous supersonic flow reactor coupled with pulsed laser photolysis and laser induced fluorescence for the production and detection of N(4S) atoms, respectively. With decreasing temperature, the experimentally measured reaction rate was found to monotonously increase up to a value of (6.6 ± 1.3) × 10−11 cm3 s−1 at 50 K. To confirm this finding, quasi-classical trajectory simulations were carried out on a previously validated, full-dimensional potential energy surface (PES). However, around 50 K the computed rates decreased which required re-evaluation of the reactive PES in the long-range part due to a small spurious barrier with a height of ∼40 K in the entrance channel. By exploring different correction schemes the measured thermal rates can be adequately reproduced, displaying a clear negative temperature dependence over the entire temperature range. The possible astrochemical implications of an increased reaction rate at low temperature are also discussed

Probing the Differential Dynamics of the Monomeric and Dimeric Insulin from Amide-I IR Spectroscopy

The monomer–dimer equilibrium for insulin is one of the essential steps in forming the receptor-binding competent monomeric form of the hormone. Despite this importance, the thermodynamic stability, in particular for modified insulins, is quite poorly understood, in part, due to experimental difficulties. This work explores one- and two-dimensional infrared spectroscopy in the range of the amide-I band for the hydrated monomeric and dimeric wild-type hormone. It is found that for the monomer the frequency fluctuation correlation function (FFCF) and the one-dimensional infrared spectra are position sensitive. The spectra of the −CO probes at the dimerization interface (residues Phe24, Phe25, and Tyr26) split and indicate an asymmetry despite the overall (formal) point symmetry of the dimer structure. Also, the decay times of the FFCF for the same −CO probe in the monomer and the dimer can differ by up to 1 order of magnitude, for example, for residue PheB24, which is solvent exposed for the monomer but at the interface for the dimer. The spectroscopic shifts correlate approximately with the average number of hydration waters and the magnitude of the FFCF at time zero. However, this correlation is only qualitative due to the heterogeneous and highly dynamical environment. Based on density functional theory calculations, the dominant contribution for solvent-exposed −CO is found to arise from the surrounding water (∼75%), whereas the protein environment contributes considerably less. The results suggest that infrared spectroscopy is a positionally sensitive probe of insulin dimerization, in particular in conjunction with isotopic labeling of the probe

The C(3P) + NO(X2Π) → O(3P) + CN(X2Σ+), N(2D)/N(4S) + CO(X1Σ+) reaction: Rates, branching ratios, and final states from 15 K to 20 000 K

The C + NO collision system is of interest in the area of high-temperature combustion and atmospheric chemistry. In this work, full dimensional potential energy surfaces for the 2 A′, 2 A″, and 4 A″ electronic states of the [CNO] system have been constructed following a reproducing kernel Hilbert space approach. For this purpose, more than 50 000 ab initio energies are calculated at the MRCI+Q/aug-cc-pVTZ level of theory. The dynamical simulations for the C( 3 P) + NO(X 2 Π) → O( 3 P) + CN(X 2 Σ + ), N( 2 D)/N( 4 S) + CO(X 1 Σ + ) reactive collisions are carried out on the newly generated surfaces using the quasiclassical trajectory (QCT) calculation method to obtain reaction probabilities, rate coefficients, and the distribution of product states. Preliminary quantum calculations are also carried out on the surfaces to obtain the reaction probabilities and compared with QCT results. The effect of nonadiabatic transitions on the dynamics for this title reaction is explored within the Landau-Zener framework. QCT simulations have been performed to simulate molecular beam experiment for the title reaction at 0.06 and 0.23 eV of relative collision energies. Results obtained from theoretical calculations are in good agreement with the available experimental as well as theoretical data reported in the literature. Finally, the reaction is studied at temperatures that are not practically achievable in the laboratory environment to provide insight into the reaction dynamics at temperatures relevant to hypersonic flight

Machine Learning for Observables: Reactant to Product State Distributions for Atom-Diatom Collisions

Machine learning-based models to predict product state distributions from a distribution of reactant conditions for atom-diatom collisions are presented and quantitatively tested. The models are based on function-, kernel- and grid-based representations of the reactant and product state distributions. While all three methods predict final state distributions from explicit quasi-classical trajectory simulations with R$^2$ > 0.998, the grid-based approach performs best. Although a function-based approach is found to be more than two times better in computational performance, the kernel- and grid-based approaches are preferred in terms of prediction accuracy, practicability and generality. The function-based approach also suffers from lacking a general set of model functions. Applications of the grid-based approach to nonequilibrium, multi-temperature initial state distributions are presented, a situation common to energy distributions in hypersonic flows. The role of such models in Direct Simulation Monte Carlo and computational fluid dynamics simulations is also discussed

Molecular-Level Understanding of the Ro-vibrational Spectra of N2_2O in Gaseous, Supercritical and Liquid SF6_6 and Xe

The transition between the gas-, supercritical-, and liquid-phase behaviour is a fascinating topic which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the vibrational spectroscopy of N$_2$O embedded in xenon and SF$_6$ as solvents provides an avenue to characterize the transitions between different phases as the concentration (or density) of the solvent increases. The present work demonstrates that classical molecular dynamics simulations together with accurate interaction potentials allows to (semi-)quantitatively describe the transition in rotational vibrational infrared spectra from the P-/R-branch lineshape for the stretch vibrations of N$_2$O at low solvent densities to the Q-branch-like lineshapes at high densities. The results are interpreted within the classical theory of rigid-body rotation in more/less constraining environments at high/low solvent densities or based on phenomenological models for the orientational relaxation of rotational motion. It is concluded that classical MD simulations provide a powerful approach to characterize and interpret the ultrafast motion of solutes in low to high density solvents at a molecular level

Accurate Reproducing Kernel-Based Potential Energy Surfaces for the Triplet Ground States of N2_2O and Dynamics for the N+NO↔\leftrightarrowO+N2_2 and N2_2+O→\rightarrow2N+O Reactions

Accurate potential energy surfaces (PESs) have been determined for the $^3$A$'$ and $^3$A$''$ states of N$_2$O using electronic structure calculations at the multireference configuration interaction level with Davidson correction (MRCI+Q) and the augmented Dunning-type correlation consistent polarize triple zeta (aug-cc-pVTZ) basis set. More than 20000 MRCI+Q/aug-cc-pVTZ energies are represented using a reproducing kernel Hilbert space (RKHS) interpolation scheme. The RKHS PESs successfully describe all reactant channels with high accuracy. The analytical PESs are characterized by computing the minima and transition states on it. Quasiclassical dynamics simulations are then used to determine thermal and vibrational relaxation rates for the N+NO and O+N$_2$ collisions. The agreement between results obtained from the simulations and from available experiments is favourable for both types of observables, which provides a test for the accuracy of the PESs. The PESs can be used to calculate more detailed state-to-state observables relevant for applications to hypersonic reentry.Comment: 32 pages, 11 figure

Exhaustive state-to-state cross sections for reactive molecular collisions from importance sampling simulation and a neural network representation

High-temperature, reactive gas flow is inherently nonequilibrium in terms of energy and state population distributions. Modeling such con- ditions is challenging even for the smallest molecular systems due to the extremely large number of accessible states and transitions between them. Here, neural networks (NNs) trained on explicitly simulated data are constructed and shown to provide quantitatively realistic descrip- tions which can be used in mesoscale simulation approaches such as Direct Simulation Monte Carlo to model gas flow at the hypersonic regime. As an example, the state-to-state cross sections for N( 4 S) + NO( 2 Π ) → O( 3 P) + N 2 (X 1 Σ + g ) are computed from quasiclassical trajectory (QCT) simulations. By training NNs on a sparsely sampled noisy set of state-to-state cross sections, it is demonstrated that independently generated reference data are predicted with high accuracy. State-specific and total reaction rates as a function of temperature from the NN are in quantitative agreement with explicit QCT simulations and confirm earlier simulations, and the final state distributions of the vibra- tional and rotational energies agree as well. Thus, NNs trained on physical reference data can provide a viable alternative to computationally demanding explicit evaluation of the microscopic information at run time. This will considerably advance the ability to realistically model nonequilibrium ensembles for network-based simulations