Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Accurate Potential Energy Surfaces for the Three Lowest Electronic States of N(2D) + H2(X1?g +) Scattering Reaction.

ABSTRACT: The three lowest full three-dimensional adiabatic and three diabatic global potential energy surfaces are reported for the title system. The accurate ab initio method (MCSCF/MRCI) with larger basis sets (aug-cc-pVQZ) is used to reduce the adiabatic potential energies, and the global adiabatic potential energy surfaces are deduced by a three-dimensional B-spline fitting method. The conical intersections and the mixing angles between the lowest three adiabatic potential energy surfaces are precisely studied. The most possible nonadiabatic reaction pathways are predicted, i.e., N(2D) + H2(X1?g +) ? NH2(22A') ? CI (12A'-22A') ? NH2(12A') ? CI (12A?-12A') ? NH2(12A?) ? NH(X3?-) + H(2S). The products of the first excited state (NH(a1?) + H(2S)) and the second excited state (NH(b1?g +) + H(2S)) can be generated in these nonadiabatic reaction pathways too.

SUBMITTER: Wang D

PROVIDER: S-EPMC6682084 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Accurate Potential Energy Surfaces for the Three Lowest Electronic States of N(2D) + H2(X1∑g +) Scattering Reaction.

Wang Dequan D Shi Guang G Fu Liwei L Yin Ruilin R Ji Youbo Y

ACS omega 20190715 7

The three lowest full three-dimensional adiabatic and three diabatic global potential energy surfaces are reported for the title system. The accurate ab initio method (MCSCF/MRCI) with larger basis sets (aug-cc-pVQZ) is used to reduce the adiabatic potential energies, and the global adiabatic potential energy surfaces are deduced by a three-dimensional B-spline fitting method. The conical intersections and the mixing angles between the lowest three adiabatic potential energy surfaces are precise ...[more]

PMID: 31460331

Similar Datasets

Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy.

Project description:Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2'-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.

| S-EPMC6568243 | biostudies-literature

Electronic Raman scattering in the 2D antiferromagnet NiPS3.

Project description:[Figure: see text].

| S-EPMC8759744 | biostudies-literature

Testing Electronic Friction Models: Vibrational De-excitation in Scattering of H2 and D2 from Cu(111).

Project description:At present, molecular dynamics with electronic friction (MDEF) is the workhorse model to go beyond the Born-Oppenheimer approximation in modeling dynamics of molecules at metal surfaces. Concomitant friction coefficients can be calculated with either the local density friction approximation (LDFA) or orbital-dependent friction (ODF), which, unlike LDFA, accounts for anisotropy while relying on other approximations. Due to the computational cost of ODF, extensive high-dimensional MDEF trajectory calculations of experimentally measurable observables have hitherto only been performed based on LDFA. We overcome this limitation with a continuous neural-network-based representation. In our first application to the scattering of vibrationally excited H2 and D2 from Cu(111), we predict up to three times higher vibrational de-excitation probabilities with ODF than with LDFA. These results indicate that anisotropic electronic friction can be important for specific molecular observables. Future experiments can test for this "fingerprint" of different approximations underlying state-of-the-art MDEF.

| S-EPMC5890313 | biostudies-literature

Global diabatic potential energy surfaces and quantum dynamical studies for the Li(2p) + H2(X(1)Σ(+)g) → LiH(X(1)Σ(+)) + H reaction.

Project description:The global diabatic potential energy surfaces which are correlated with the ground state 1A' and the excited state 2A' of the Li(2p) + H2 reaction are presented in this study. The multi-reference configuration interaction method and large basis sets (aug-cc-pVQZ for H atom and cc-pwCVQZ for Li atom) were employed in the ab initio single-point energy calculations. The diabatic potential energies were generated by the diabatization scheme based on transition dipole moment operators. The neural network method was utilized to fit the matrix elements of the diabatic energy surfaces, and the root mean square errors were extremely small (3.69 meV for , 5.34 meV for and 5.06 meV for ). The topographical features of the diabatic potential energy surfaces were characterized and the surfaces were found to be sufficiently smooth for the dynamical calculation. The crossing seam of the conical intersections between the and surfaces were pinpointed. Based on this new analytical diabatic potential energy surfaces, time-dependent wave packet calculation were conducted to investigate the mechanism of the title reaction. At low collision energies, the product LiH molecule tends to forward scattering, while at high collision energies, the forward and backward scatterings exist simultaneously.

| S-EPMC4850413 | biostudies-other

Energy harvesting from enzymatic biowaste reaction through polyelectrolyte functionalized 2D nanofluidic channels.

Project description:Effective recycling of biowaste energy in a compact system remains a great challenge. Here, we report a graphene-based energy harvesting system powered by enzymatic biowaste reaction through two-dimensional (2D) nanofluidic channels. The integrated 2D nanofluidic generator shows distinct advantages such as flexibility, low cost, and high output in ionic currents.

| S-EPMC6008704 | biostudies-other

Ground state potential energy surfaces around selected atoms from resonant inelastic x-ray scattering.

Project description:Thermally driven chemistry as well as materials' functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future.

| S-EPMC4731820 | biostudies-other

Quantum coherence selective 2D Raman-2D electronic spectroscopy.

Project description:Electronic and vibrational correlations report on the dynamics and structure of molecular species, yet revealing these correlations experimentally has proved extremely challenging. Here, we demonstrate a method that probes correlations between states within the vibrational and electronic manifold with quantum coherence selectivity. Specifically, we measure a fully coherent four-dimensional spectrum which simultaneously encodes vibrational-vibrational, electronic-vibrational and electronic-electronic interactions. By combining near-impulsive resonant and non-resonant excitation, the desired fifth-order signal of a complex organic molecule in solution is measured free of unwanted lower-order contamination. A critical feature of this method is electronic and vibrational frequency resolution, enabling isolation and assignment of individual quantum coherence pathways. The vibronic structure of the system is then revealed within an otherwise broad and featureless 2D electronic spectrum. This method is suited for studying elusive quantum effects in which electronic transitions strongly couple to phonons and vibrations, such as energy transfer in photosynthetic pigment-protein complexes.

| S-EPMC5353627 | biostudies-literature

Switchable scattering meta-surfaces for broadband terahertz modulation.

Project description:Active tuning and switching of electromagnetic properties of materials is of great importance for controlling their interaction with electromagnetic waves. In spite of their great promise, previously demonstrated reconfigurable metamaterials are limited in their operation bandwidth due to their resonant nature. Here, we demonstrate a new class of meta-surfaces that exhibit electrically-induced switching in their scattering parameters at room temperature and over a broad range of frequencies. Structural configuration of the subwavelength meta-molecules determines their electromagnetic response to an incident electromagnetic radiation. By reconfiguration of the meta-molecule structure, the strength of the induced electric field and magnetic field in the opposite direction to the incident fields are varied and the scattering parameters of the meta-surface are altered, consequently. We demonstrate a custom-designed meta-surface with switchable scattering parameters at a broad range of terahertz frequencies, enabling terahertz intensity modulation with record high modulation depths and modulation bandwidths through a fully integrated, voltage-controlled device platform at room temperature.

| S-EPMC4099982 | biostudies-literature

Toward Accurate Adsorption Energetics on Clay Surfaces.

Project description:Clay minerals are ubiquitous in nature, and the manner in which they interact with their surroundings has important industrial and environmental implications. Consequently, a molecular-level understanding of the adsorption of molecules on clay surfaces is crucial. In this regard computer simulations play an important role, yet the accuracy of widely used empirical force fields (FF) and density functional theory (DFT) exchange-correlation functionals is often unclear in adsorption systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water and methanol adsorption on the prototypical clay kaolinite. To the best of our knowledge, this is the first time QMC has been used to investigate adsorption at a complex, natural surface such as a clay. As well as being valuable in their own right, the QMC benchmarks obtained provide reference data against which the performance of cheaper DFT methods can be tested. Indeed using various DFT exchange-correlation functionals yields a very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in the systems considered here it is essential to account for van der Waals (vdW) dispersion forces since this alters both the absolute and relative adsorption energies of water and methanol. We show, via FF simulations, that incorrect relative energies can lead to significant changes in the interfacial densities of water and methanol solutions at the kaolinite interface. Despite the clear improvements offered by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption energies are often overestimated, suggesting that the treatment of vdW forces in DFT is not yet a solved problem.

| S-EPMC5126707 | biostudies-literature

Non-resonant light scattering in dispersions of 2D nanosheets.

Project description:Extinction spectra of nanomaterial suspensions can be dominated by light scattering, hampering quantitative spectral analysis. No simple models exist for the wavelength-dependence of the scattering coefficients in suspensions of arbitrary-sized, high-aspect-ratio nanoparticles. Here, suspensions of BN, talc, GaS, Ni(OH)2, Mg(OH)2 and Cu(OH)2 nanosheets are used to explore non-resonant scattering in wide-bandgap 2D nanomaterials. Using an integrating sphere, scattering coefficient (?) spectra were measured for a number of size-selected fractions for each nanosheet type. Generally, ? scales as a power-law with wavelength in the non-resonant regime: ?(?)?[?/?L?]-m, where ?L? is the mean nanosheet length. For all materials, the scattering exponent, m, forms a master-curve, transitioning from m?=?4 to m?=?2, as the characteristic nanosheet area increases, indicating a transition from Rayleigh to van der Hulst scattering. In addition, once material density and refractive index are factored out, the proportionality constant relating ? to [?/?L?]-m, also forms a master-curve when plotted versus ?L?.

| S-EPMC6212482 | biostudies-literature