☆ 4.7 Article

An ab initio based full-dimensional global potential energy surface for FH2O(X2A′)and dynamics for the F + H2O → HF plus HO reaction

JOURNAL OF CHEMICAL PHYSICS (2012)

获取全文
添加到收藏夹

期刊

JOURNAL OF CHEMICAL PHYSICS
卷 137, 期 9, 页码 -

出版社

AMER INST PHYSICS
DOI: 10.1063/1.4748857

关键词

-

类别

Chemistry, Physical Physics, Atomic, Molecular & Chemical

资金

  1. US Department of Energy [DE-FG02-05ER15694]
  2. Missouri Research Board

向作者/读者索取更多资源

Protocol

社区支持

Reagent

社区支持

A global potential energy surface (PES) for the ground electronic state of FH2O is constructed based on more than 30 000 ab initio points at the multi-reference configuration interaction level. The PES features a pre-reaction van der Waals well and two post-reaction hydrogen-bonded complexes, as well as a reactant-like transition state with a classical barrier of 3.8 kcal/mol. The adiabatic F + H2O -> HF + OH reaction dynamics on this PES was investigated using a standard quasi-classical trajectory method. In agreement with experiment, the HF product contains significant vibrational excitation with limited rotational excitation, while the OH product is internally cold, reflecting its spectator role in the reaction. The products are primarily scattered in the backward direction, consistent with a direct abstraction mechanism. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4748857]

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

Article Chemistry, Physical

Hyperthermal Dynamics and Kinetics of the C(3P)+N2(X1? +g) ? CN(X2? +) + N(4S) Reaction

Dandan Lu, Rodrigo Urzua-Leiva, Otoniel Denis-Alpizar, Hua Guo

Summary: The hyperthermal dynamics and kinetics of the title reaction, which plays an important role in hypersonic chemistry for atmospheric entry vehicles, are investigated using quasi-classical trajectory methods on a recently developed ground electronic state potential energy surface. The dynamics calculations indicated that the reaction follows a complex-forming mechanism, despite its large endoergicity. The calculated differential cross section is forward-backward symmetric, consistent with a long-lived reaction intermediate supported by the NCN potential well . The lifetime of the reaction complex is sufficiently long that the vibrational distribution of the CN product can be predicted by the phase space theory. The calculated vibrational state specific and thermal rate coefficients follow the Arrhenius behavior, and the agreement with existing low-temperature experimental thermal rate coefficients is satisfactory. Extrapolations to high temperatures relev a n t to hypersonic conditions are provided.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

添加到收藏夹
Article Chemistry, Physical

Quantum and Semiclassical Dynamics of Nonadiabatic Electronic Excitation of C(3P) to C1D) by Hyperthermal Collisions with N2

Dandan Lu, Hua Guo

Summary: The dynamics and kinetics of nonadiabatic excitation of C(3P) to C(1D) induced by hyperthermal collisions with N2 molecules were investigated using quantum mechanical and two semiclassical nonadiabatic methods. The interaction potential energy surfaces and spin-orbit coupling were represented by a diabatic potential energy matrix, which facilitated the spin-forbidden process. Quantum dynamics calculations showed small transition probabilities due to weak spin-orbit coupling, with the most favored spin-flip transition near the threshold. The results also revealed strong oscillations and vibrational state-specified rate coefficients, with the N2 collision partner increasing the excitation rate at low temperatures but reversing the trend at high temperatures. The semiclassical methods qualitatively reproduced the quantum rate coefficients.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

添加到收藏夹
Article Chemistry, Physical

Activation of Methane by Zr plus : A Deep-Dive into the Potential Surface via Pressure- and Temperature-Dependent Kinetics with Statistical Modeling

Brendan C. Sweeny, Bryan A. Long, Dominique Maffucci, Junxiang Zuo, Hua Guo, Albert A. Viggiano, Shaun G. Ard, Nicholas S. Shuman

Summary: The kinetics of the reaction between Zr+ and CH4 were investigated over a range of temperatures and pressures using a selected-ion flow tube apparatus. The measured rate constants were found to be small, indicating that the reaction is not very efficient. Two products, ZrCH4+ and ZrCH2+, were observed. A statistical modeling approach was used to fit the experimental data and revealed important information about the reaction mechanism and energetics. The results showed that the formation of the bimolecular product is favored over competing processes, and the energy of the products and reaction depend on various factors.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

添加到收藏夹
Article Chemistry, Physical

Cold Collisions of Ro-Vibrationally Excited D2 Molecules

James F. E. Croft, Pablo G. Jambrina, F. Javier Aoiz, Hua Guo, N. Balakrishnan

Summary: This study focuses on the collisions of two D2 molecules prepared in the v = 2 vibrational level and j = 2 rotational level. Quantum calculations were performed to identify key resonance features that contribute to the angular distribution in the experimental results.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

添加到收藏夹
Article Chemistry, Physical

Post-dissociation Dynamics of N2 on Ru(0001): How Far Can the Hot N Atoms Travel?

Hua Guo, Yingqi Wang

Summary: As shown by a recent scanning tunneling microscopy study, the dissociation of N-2 impinging on Ru(0001) produces spherical N atoms that can travel significant distances from the impact site. In this work, the hot nitrogen atom dynamics following N-2 dissociation is investigated theoretically using a neural network representation of density functional theory data. Quasi-classical trajectory simulations reveal that typically only one N atom undergoes significant migration, while the other is often trapped near the impact site. The relatively short migration distance of the hot N atom found in the simulations is attributed to a high diffusion barrier and fast energy dissipation to surface phonons.

JOURNAL OF PHYSICAL CHEMISTRY C (2023)

添加到收藏夹
Article Chemistry, Physical

SO2 Photodissociation at 193 nm Directly Forms S(3P) + O2(3Sg-): Implications for the Archean Atmosphere on Earth

Daniel Rosch, Yifei Xu, Hua Guo, Xixi Hu, David L. Osborn

Summary: We provide experimental evidence of a new photodissociation pathway of SO2, resulting in the production of S(P-3(j)) + O-2 X(S-3(g)-) with a yield of 2-4%. High-level ab initio calculations suggest that this pathway occurs through internal conversion from the excited state followed by isomerization to a transient SOO intermediate. Classical trajectory simulations qualitatively reproduce the experimental yields, indicating the significance of this unexpected photodissociation pathway in understanding Earth's geologic history and atmospheric evolution.

JOURNAL OF PHYSICAL CHEMISTRY LETTERS (2023)

添加到收藏夹
Article Chemistry, Multidisciplinary

Direct or Precursor-Mediated? Mechanisms for Methane Dissociation on Pt(110)-(2 x 1) at Both Low and High Incidence Energies

Fenfei Wei, Sen Lin, Hua Guo

Summary: This paper presents a theoretical investigation of methane dissociation on a Pt(110)-(2 x 1) surface using a machine-learned potential energy surface. The simulations show good agreement with experimental results at high incidence energies and provide an explanation for negative activation at low incidence energies.

JACS AU (2023)

添加到收藏夹
Article Chemistry, Physical

Theoretical Insights into the Dynamics of Gas-Phase Bimolecular Reactions with Submerged Barriers

Hongwei Song, Hua Guo

Summary: This Perspective focuses on the dynamics of gas-phase bimolecular reactions with submerged barriers, which are prevalent in combustion, atmospheric chemistry, astrochemistry, and plasma chemistry. The temperature dependence of the rate coefficients for such reactions is often non-Arrhenius and complex, and the corresponding dynamics may also be quite different from those with significant barriers or those completely dominated by capture. Recent experimental and theoretical studies have revealed interesting dynamical behaviors, particularly at relatively low temperatures or collision energies, enriching our understanding of these unusual reactions.

ACS PHYSICAL CHEMISTRY AU (2023)

添加到收藏夹
Article Chemistry, Physical

Quantum and semiclassical studies of nonadiabatic electronic transitions between N(4S) and N(2D) by collisions with N2

Dandan Lu, Breno R. L. Galvao, Antonio J. C. Varandas, Hua Guo

Summary: The dynamics and kinetics of spin-forbidden transitions between N(D-2) and N(S-4) mediated by collisions with N-2 molecules were investigated using quantum wave packet (WP) method and semi-classical coherent switches with decay of mixing (CSDM) method. These transitions compete with exchange reaction channels on both doublet and quartet potential energy surfaces. The WP and CSDM quenching rate coefficients were in reasonable agreement with each other, reproducing previous theoretical results. For the excitation process, the agreement between the two approaches depended on the treatment of zero-point energy (ZPE) in the product, as the high endoergicity of this process led to severe violation of vibrational ZPE. The Gaussian-binning (GB) method improved the agreement with the quantum result. The excitation rate coefficients were two orders of magnitude smaller than those of the adiabatic exchange reaction, indicating inefficient intersystem crossing due to weak spin-orbit coupling between the two spin manifolds of the N-3 system.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2023)

添加到收藏夹
Article Chemistry, Physical

Informing air-carbon ablation modeling with theoretical calculations of atomic oxygen and nitrogen interacting with carbon surfaces

Reed Nieman, Michael Sands, Yingqi Wang, Timothy K. Minton, Erin E. Mussoni, Jeffrey Engerer, Hua Guo

Summary: In order to investigate the gas-surface chemistry on the thermal protection system of a hypersonic vehicle, extensive periodic density functional theory (DFT) calculations are conducted to study the interaction between atomic oxygen/nitrogen and highly oriented pyrolytic graphite (HOPG) surfaces. The calculated reaction energies and barriers provide important information for adsorption, desorption, diffusion, recombination, and other reactions. The results are compared with a finite-rate model and suggest that some model parameters may need further refinement. These calculations contribute to the development of a predictive kinetic model for the complex reaction network under hypersonic flight conditions.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2023)

添加到收藏夹
Article Chemistry, Physical

The Li plus CaF → Ca plus LiF chemical reaction under cold conditions

Humberto da Silva Jr, Qian Yao, Masato Morita, Brian K. Kendrick, Hua Guo, Naduvalath Balakrishnan

Summary: This paper reports the ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF -> LiF + Ca chemical reaction. The results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule, and the reaction is inefficient in the 1-100 mK regime, allowing sympathetic cooling of CaF by collisions with cold Li atoms.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2023)

添加到收藏夹
Article Chemistry, Physical

Post-dissociation Dynamics of N2 on Ru(1000): How Far Can the ?Hot? N Atoms Travel?

Yingqi Wang, Hua Guo

Summary: A recent study using scanning tunneling microscopy showed that N2 dissociation on Ru(0001) generates N atoms with high exoergicity, which can migrate away from the impact site. In this work, theoretical investigation based on a high-dimensional potential energy surface and neural network representation was conducted to study the dynamics of these hot nitrogen atoms. Simulation results revealed that typically only one N atom undergoes significant migration while the other remains near the impact site. The average final separation between the two N atoms is much smaller than the experimental report, mainly attributed to high diffusion barrier and fast energy dissipation to surface phonons.

JOURNAL OF PHYSICAL CHEMISTRY C (2023)

添加到收藏夹
Article Chemistry, Physical

High-accuracy DMBE potential energy surface for CNO(4 A′′) and the rate coefficients for the C plus NO reaction in the 2 A′, 2 A, and 4 A′′ states

Marcio O. Alves, Vinicius C. Mota, Joao P. Braga, Antonio J. C. Varandas, Hua Guo, Breno R. L. Galvao

Summary: In this study, an accurate potential energy surface (PES) for the lowest lying (4 )A '' state of the CNO system is presented. The energy terms are fitted using a theoretical framework, incorporating long-range interactions. The results show improved accuracy in predicting rate coefficients and highlight the importance of long-range interactions for low-temperature reactions.

JOURNAL OF CHEMICAL PHYSICS (2023)

添加到收藏夹
Article Chemistry, Physical

Quantum Dynamics of Photodissociation: Recent Advances and Challenges

Shanyu Han, Changjian Xie, Xixi Hu, David R. Yarkony, Hua Guo, Daiqian Xie

Summary: Recent advances in quantum mechanical studies of adiabatic and nonadiabatic photodissociation dynamics have provided new insights into initial state control and product energy disposal. These insights have helped to understand quantum effects in small prototypical systems and serve as benchmarks for developing more approximate theoretical methods.

JOURNAL OF PHYSICAL CHEMISTRY LETTERS (2023)

添加到收藏夹
Article Chemistry, Physical

Toward a Unified Analytical Description of Internal Conversion and Intersystem Crossing in the Photodissociation of Thioformaldehyde. I. Diabatic Singlet States

Yafu Guan, Changjian Xie, Hua Guo, David R. Yarkony

Summary: The article reports the diabatic potential energy matrix (DPEM) for the two singlet states (S-0 and S-1) of thioformaldehyde, which is constructed based on high-level multireference configuration interaction wave functions. The saturated H-d in the molecular configuration space provides an accurate description of the photodissociation of thioformaldehyde on its singlet states and is essential for incorporating spin-orbit couplings into a unified framework.

JOURNAL OF CHEMICAL THEORY AND COMPUTATION (2023)

添加到收藏夹
暂无数据
研讨会 海报 问题 讨论圈 基金 期刊 论文 科研社交 资讯集成 审稿人 关于我们 常见问题 移动App 隐私条款 使用条款
© Peeref 2019-2024. All rights reserved.