scholarly journals Unexpected dynamical effects change the lambda-doublet propensity in the tunneling region for the O(3P) + H2 reaction

2019 ◽  
Vol 21 (45) ◽  
pp. 25389-25396
Author(s):  
P. G. Jambrina ◽  
A. Zanchet ◽  
M. Menéndez ◽  
V. J. Herrero ◽  
F. J. Aoiz
Keyword(s):  
Transition State ◽  
Reactive Flux

The present calculations for the O(3P) + H2 reaction show that the A′′ is more reactive than the A′ PES. However, at energies close to the vibrationally adiabatic barrier for H2 in j = 0, the reactive flux is larger on A′ PES due to a reorienting effect that promotes collinear approaches at the transition state.

First principles rates for surface chemistry employing exact transition state theory: application to recombinative desorption of hydrogen from Cu(111)

2020 ◽  
Vol 22 (31) ◽  
pp. 17532-17539 ◽  
Author(s):  
Oihana Galparsoro ◽  
Sven Kaufmann ◽  
Daniel J. Auerbach ◽  
Alexander Kandratsenka ◽  
Alec M. Wodtke
Keyword(s):  
Transition State ◽  
Surface Chemistry ◽  
First Principles ◽  
Transition State Theory ◽  
State Theory ◽  
First Principles Calculations ◽  
Theory Application ◽  
Reactive Flux

We present first principles calculations of the reactive flux for thermal recombinative desorption of hydrogen from Cu(111).

Memapsin 2, a drug target for Alzheimer's disease

2003 ◽  
Vol 70 ◽  
pp. 213-220 ◽  
Author(s):  
Gerald Koelsch ◽  
Robert T. Turner ◽  
Lin Hong ◽  
Arun K. Ghosh ◽  
Jordan Tang
Keyword(s):  
Crystal Structure ◽  
Alzheimer’S Disease ◽  
Alzheimer's Disease ◽  
Transition State ◽  
Amyloid Precursor Protein ◽  
Therapeutic Target ◽  
Drug Target ◽  
Aspartic Protease ◽  
Precursor Protein ◽  
Memapsin 2

Mempasin 2, a ϐ-secretase, is the membrane-anchored aspartic protease that initiates the cleavage of amyloid precursor protein leading to the production of ϐ-amyloid and the onset of Alzheimer's disease. Thus memapsin 2 is a major therapeutic target for the development of inhibitor drugs for the disease. Many biochemical tools, such as the specificity and crystal structure, have been established and have led to the design of potent and relatively small transition-state inhibitors. Although developing a clinically viable mempasin 2 inhibitor remains challenging, progress to date renders hope that memapsin 2 inhibitors may ultimately be useful for therapeutic reduction of ϐ-amyloid.

Collisional dynamics of Ca1D + HBr reactions: evidence for transition-state motions

1999 ◽  
Vol 97 (8) ◽  
pp. 967-976 ◽  
Author(s):  
M. Garay Salazar, J. M. Orea Rocha, A.
Keyword(s):  
Transition State ◽  
Collisional Dynamics

Reactions of an Aluminium(I) Reagent with 1,2-, 1,3- and 1,5-Dienes: Dearomatisation, Reversibility, and a Pericyclic Mechanism

2019 ◽  
Author(s):  
Clare Bakewell ◽  
Martí Garçon ◽  
Richard Y Kong ◽  
Louisa O'Hare ◽  
Andrew J. P. White ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Transition State ◽  
Reaction Pathways ◽  
Aromatic Rings ◽  
Aromatic Character ◽  
Pericyclic Reaction

The reactions of an aluminium(I) reagent with a series of 1,2-, 1,3- and 1,5-dienes are reported. In the case of 1,3-dienes the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene containing products. This mechanism has been interrogated by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4+1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4+1) cycloaddition includes dienes that are either in part, or entirely, contained within aromatic rings. In these cases, reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2- or 1,5-dienes complementary reactivity is observed; the orthogonal nature of the C=C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavour a (4+1) cycloaddition. Rather, reaction pathways are determined by an initial (2+1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C=C π-bond leading to complex organometallic products that incorporate fused hydrocarbon rings.

Active Learning Accelerates Ab Initio Molecular Dynamics on Pericyclic Reactive Energy Surfaces

2020 ◽  
Author(s):  
Shi Jun Ang ◽  
Wujie Wang ◽  
Daniel Schwalbe-Koda ◽  
Simon Axelrod ◽  
Rafael Gomez-Bombarelli
Keyword(s):  
Molecular Dynamics ◽  
Potential Energy ◽  
Transition State ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Energy Surface ◽  
Computational Cost ◽  
Reactive Trajectories ◽  
Dynamics Simulations ◽  
Energy Surfaces

<div>Modeling dynamical effects in chemical reactions, such as post-transition state bifurcation, requires <i>ab initio</i> molecular dynamics simulations due to the breakdown of simpler static models like transition state theory. However, these simulations tend to be restricted to lower-accuracy electronic structure methods and scarce sampling because of their high computational cost. Here, we report the use of statistical learning to accelerate reactive molecular dynamics simulations by combining high-throughput ab initio calculations, graph-convolution interatomic potentials and active learning. This pipeline was demonstrated on an ambimodal trispericyclic reaction involving 8,8-dicyanoheptafulvene and 6,6-dimethylfulvene. With a dataset size of approximately</div><div>31,000 M062X/def2-SVP quantum mechanical calculations, the computational cost of exploring the reactive potential energy surface was reduced by an order of magnitude. Thousands of virtually costless picosecond-long reactive trajectories suggest that post-transition state bifurcation plays a minor role for the reaction in vacuum. Furthermore, a transfer-learning strategy effectively upgraded the potential energy surface to higher</div><div>levels of theory ((SMD-)M06-2X/def2-TZVPD in vacuum and three other solvents, as well as the more accurate DLPNO-DSD-PBEP86 D3BJ/def2-TZVPD) using about 10% additional calculations for each surface. Since the larger basis set and the dynamic correlation capture intramolecular non-covalent interactions more accurately, they uncover longer lifetimes for the charge-separated intermediate on the more accurate potential energy surfaces. The character of the intermediate switches from entropic to thermodynamic upon including implicit solvation effects, with lifetimes increasing with solvent polarity. Analysis of 2,000 reactive trajectories on the chloroform PES shows a qualitative agreement with the experimentally-reported periselectivity for this reaction. This overall approach is broadly applicable and opens a door to the study of dynamical effects in larger, previously-intractable reactive systems.</div>

An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

2020 ◽  
Author(s):  
Veejendra Yadav
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Lower Energy ◽  
Aldol Reaction ◽  
Membered Ring ◽  
Ammonium Ion ◽  
Alternate Energy ◽  
Ring Transition State ◽  
Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

An Alternate Energy-Conserved Pathway for the Morita-Baylis-Hillman (MBH) Reaction

2020 ◽  
Author(s):  
Veejendra Yadav
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Lower Energy ◽  
Aldol Reaction ◽  
Membered Ring ◽  
Ammonium Ion ◽  
Alternate Energy ◽  
Ring Transition State ◽  
Mbh Reaction

An new overall lower energy pathway for the amine-catalysed Morita-Baylis-Hillman reaction is proposed from computations at the M06-2X/6-311++G(d,p) level. The pathway involves proton-transfer from the ammonium ion to the alkoxide formed from the aldol reaction through a seven-membered ring transition state (TS) structure followed by highly exothermic Hofmann<i> </i>elimination through a five-membered ring TS structure to form the product and also release the catalyst to carry on with the process all over again.

On the Conrotatory Ring Opening of 3-Carbomethoxycyclobutene Vis-À-Vis 3-Carbomethoxy-1,2-Benzocyclobutene and the Predominant Inward Opening of 3-Dimethylaminocarbonyl-1,2-Benzocyclobutene

2018 ◽  
Author(s):  
Veejendra Yadav ◽  
Dasari L V K Prasad ◽  
Arpita Yadav ◽  
Maddali L N Rao
Keyword(s):  
Transition State ◽  
Ring Opening ◽  
Electron Process ◽  
Ring Opening Reaction ◽  
Stable Species ◽  
Electron Event

<p>The torquoselectivity of conrotatory ring opening of 3-carbomethoxycyclobutene is controlled by p<sub>C1C2</sub>→s*<sub>C3C4</sub> and s<sub>C3C4</sub>→p*<sub>CO</sub> interactions in the transition state in a 4-electron process as opposed to only s<sub>C3C4</sub>→p*<sub>CO</sub> interaction in an apparently 8-electron event in 3-carbomethoxy-1,2-benzocyclobutene. The ring opening of 3-carbomethoxy-1,2-benzocyclobutene is sufficiently endothermic. We therefore argue that the reverse ring closing reaction is faster than the forward ring opening reaction and, thus, it establishes an equilibrium between the two and subsequently allows formation of the more stable species <i>via</i> outward ring opening reaction. Application of this argument to 3-dimethylaminocarbonyl-1,2-benzocyclobutene explains the predominantly observed inward opening.</p>

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