Theoretical Chemistry Accounts最新文献_第8页

A trajectory surface hopping study of the vibration-induced autodetachment dynamics of the 1-nitropropane anion 1-硝基丙烷阴离子振动诱导自脱离动力学的轨迹表面跳变研究

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Theoretical Chemistry Accounts Pub Date : 2023-11-08 DOI: 10.1007/s00214-023-03063-z

Kevin Issler, Roland Mitric, Jens Petersen

{"title":"A trajectory surface hopping study of the vibration-induced autodetachment dynamics of the 1-nitropropane anion","authors":"Kevin Issler, Roland Mitric, Jens Petersen","doi":"10.1007/s00214-023-03063-z","DOIUrl":"https://doi.org/10.1007/s00214-023-03063-z","url":null,"abstract":"Abstract In this study, we investigate the autodetachment dynamics of the 1-nitropropane anion after vibrational excitation of the energetically lowest C–H stretching mode using our recently developed extended quantum classical surface hopping approach including the detachment continuum. Therein the detachment from an electronic bound anion state is treated as a nonadiabatic transition into discretized detachment continuum states for an ensemble of classical nuclear trajectories propagated on quantum mechanical potential energy surfaces. The initial ensemble is obtained by sampling a phase space distribution accounting for the vibrational excitation of the C–H stretching mode of the molecule to match the experimental conditions. The simulated kinetic energy distribution of the ejected electrons reproduces characteristic features of the available experimental data. Analysis of the nuclear dynamics points out that the approach to neutral-like geometries with decreased pyramidalization angle of the NO $$_2$$ <mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:msub> <mml:mrow /> <mml:mn>2</mml:mn> </mml:msub> </mml:math> group and reduced the N–O bond lengths are the crucial factors enhancing the ultrafast autodetachment process in vibrationally excited 1-nitropropane. This is facilitated when the dipole-bound first excited state of the anion is populated, which is structurally similar to the neutral system. Although only a small transient population of this state is observed, it acts as an efficient doorway to the detachment continuum and is responsible for a significant amount of the ejected electrons.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"25 37","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135391695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1

N- and C-diallyl monomers of new structural types in radical polymerization: theoretical study on the mechanism of reaction 自由基聚合新结构类型的N-和c -二烯丙基单体:反应机理的理论研究

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Theoretical Chemistry Accounts Pub Date : 2023-11-01 DOI: 10.1007/s00214-023-03067-9

Marina Gorbunova, Sergey Shurov, Aleksandr Vasyanin, Vladimir Strelnikov

引用次数: 0

QTAIM view of Fe…Fe binding within triiron clusters [(μ3-S) Fe3(CO)9(μ3-CO)] 铁在三铁团簇中的结合[(μ3-S) Fe3(CO)9(μ3-CO)]

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Theoretical Chemistry Accounts Pub Date : 2023-10-30 DOI: 10.1007/s00214-023-03065-x

Noorhan Ali Hamza, Muhsen Abood Muhsen Al-Ibadi

引用次数: 0

On the decomposition mechanism of propanal: rate constants evaluation and kinetic simulations 丙醛分解机理研究:速率常数评估及动力学模拟

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Theoretical Chemistry Accounts Pub Date : 2023-10-26 DOI: 10.1007/s00214-023-03060-2

Andrea Della Libera, Maristella Di Teodoro, Matteo Pelucchi, Carlo Cavallotti

{"title":"On the decomposition mechanism of propanal: rate constants evaluation and kinetic simulations","authors":"Andrea Della Libera, Maristella Di Teodoro, Matteo Pelucchi, Carlo Cavallotti","doi":"10.1007/s00214-023-03060-2","DOIUrl":"https://doi.org/10.1007/s00214-023-03060-2","url":null,"abstract":"Abstract The reactivity of aldehydes has been the subject of considerable interest in chemical kinetics, with propanal often chosen as the representative species. Despite its relevance, the reactivity of propanal is currently estimated from analogy and fitting of experimental data measured in limited temperature and pressure ranges, while the few literature theoretical studies have focused more on the exploration the potential energy surface (PES) than on the estimation of rate constants. The purpose of this work is to reinvestigate the propanal decomposition kinetics using the ab initio transition state theory based master equation approach with the intent of: (1) Determining accurate rate constants of key reaction channels; (2) Updating and validating an existing kinetic model by simulating available experimental data on propanal pyrolysis. It is found that propanal decomposition at the initial stages of pyrolysis occurs through four unimolecular barrierless reactions to form CHO + C 2 H 5 , CH 2 CHO + CH 3 , CH 3 CHCHO + H, and CH 3 CH 2 CO + H, and a termolecular pathway leading to the formation of C 2 H 4 + CO + H 2 . High pressure rate constants were determined for each barrierless reaction channel using Variable Reaction Coordinate Transition State Theory and used to estimate phenomenological temperature and pressure dependent channel specific rate constants integrating the 1 dimensional master equation over the whole PES. The decomposition rate constants so determined are in agreement with the few available experimental data and significantly faster than previous literature estimates. The estimated kinetic parameters were finally implemented into the CRECK kinetic mechanism, leading to an improved agreement with shock tube pyrolysis data from the literature.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"53 3","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134907193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

IQA analysis of the two-particle density matrix: chemical insight and computational efficiency 双粒子密度矩阵的IQA分析:化学洞察力和计算效率

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Theoretical Chemistry Accounts Pub Date : 2023-10-26 DOI: 10.1007/s00214-023-03057-x

Mark A. Vincent, Paul L. A. Popelier

引用次数: 0

A theoretical study for spin-dependent hydrogen abstraction by non-heme FeIVO complexes based on DFT potential energy surfaces 基于DFT势能面的非血红素FeIVO配合物自旋依赖吸氢的理论研究

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Theoretical Chemistry Accounts Pub Date : 2023-10-24 DOI: 10.1007/s00214-023-03059-9

Sumin Park, Binh Khanh Mai, Yongho Kim

引用次数: 0

Binding patterns of derivatives of fisetin and chrysin to the enzyme complex cyclin-dependent kinase 6/cyclin D 非瑟酮和菊花素衍生物与周期蛋白依赖性激酶6/周期蛋白D酶复合物的结合模式

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Theoretical Chemistry Accounts Pub Date : 2023-10-19 DOI: 10.1007/s00214-023-03043-3

Srutishree Sarma, Nand Kishor Gour, Dikshita Dowerah, Saheen Shehnaz Begum, Ramesh Chandra Deka

引用次数: 0

Thermodynamic investigation on ion structure and conductivity of LiF–NdF3 molten salt LiF-NdF3熔盐离子结构和电导率的热力学研究

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Theoretical Chemistry Accounts Pub Date : 2023-10-18 DOI: 10.1007/s00214-023-03056-y

ZanHui Fu, ChunFa Liao, Xu Wang, GengFeng Deng, Xun Zhou, LiangHua Que

引用次数: 0

Experimental spectroscopic and molecular docking investigations of the anticancer drugs aprepitant and capecitabine 抗癌药物阿瑞吡坦和卡培他滨的实验光谱和分子对接研究

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Theoretical Chemistry Accounts Pub Date : 2023-10-14 DOI: 10.1007/s00214-023-03055-z

P. Venkata Ramana

引用次数: 0

Structures, stabilities and electronic properties of nitrogen dioxide adsorbed and embedded boron nitride clusters with different diameters 二氧化氮吸附和包埋不同直径氮化硼团簇的结构、稳定性和电子性能

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Theoretical Chemistry Accounts Pub Date : 2023-10-14 DOI: 10.1007/s00214-023-03058-w

Zhi Li, Jia-cong Li, Jia-hui Yin, Shu-qi Yang, Zhen Zhao

引用次数: 0