Machine Learning Estimation of Atom Condensed Fukui Functions

2015 ◽  
Vol 35 (2) ◽  
pp. 62-69 ◽  
Author(s):  
Qingyou Zhang ◽  
Fangfang Zheng ◽  
Tanfeng Zhao ◽  
Xiaohui Qu ◽  
João Aires-de-Sousa
Keyword(s):  
Machine Learning ◽  
Fukui Functions ◽  
Condensed Fukui Functions

scholarly journals DFT investigations on arylsulphonyl pyrazole derivatives as potential ligands of selected kinases

2020 ◽  
Vol 18 (1) ◽  
pp. 857-873
Author(s):  
Kornelia Czaja ◽  
Jacek Kujawski ◽  
Radosław Kujawski ◽  
Marek K. Bernard
Keyword(s):  
Free Energy ◽  
Molecular Orbital ◽  
Density Functional ◽  
Chemical Reactivity ◽  
Chemical Hardness ◽  
Free Energy Of Solvation ◽  
Fukui Functions ◽  
Reactivity Descriptors ◽  
Condensed Fukui Functions ◽  
Charge Partitioning

AbstractUsing the density functional theory (DFT) formalism, we have investigated the properties of some arylsulphonyl indazole derivatives that we studied previously for their biological activity and susceptibility to interactions of azoles. This study includes the following physicochemical properties of these derivatives: electronegativity and polarisability (Mulliken charges, adjusted charge partitioning, and iterative-adjusted charge partitioning approaches); free energy of solvation (solvation model based on density model and M062X functional); highest occupied molecular orbital (HOMO)–lowest occupied molecular orbital (LUMO) gap together with the corresponding condensed Fukui functions, time-dependent DFT along with the UV spectra simulations using B3LYP, CAM-B3LYP, MPW1PW91, and WB97XD functionals, as well as linear response polarisable continuum model; and estimation of global chemical reactivity descriptors, particularly the chemical hardness factor. The charges on pyrrolic and pyridinic nitrogen (the latter one in the quinolone ring of compound 8, as well as condensed Fukui functions) reveal a significant role of these atoms in potential interactions of azole ligand–protein binding pocket. The lowest negative value of free energy of solvation can be attributed to carbazole 6, whereas pyrazole 7 has the least negative value of this energy. Moreover, the HOMO–LUMO gap and chemical hardness show that carbazole 6 and indole 5 exist as soft molecules, while fused pyrazole 7 has hard character.

Application of Condensed Fukui Functions to Cobalt Macrocycle Complexes

2003 ◽  
Vol 107 (51) ◽  
pp. 11483-11488 ◽  
Author(s):  
Gloria I. Cárdenas-Jirón ◽  
Eduardo Parra-Villalobos
Keyword(s):  
Fukui Functions ◽  
Condensed Fukui Functions

Experimental and Theoretical Investigation of the Reaction of Secondary Amines with Maleic Anhydride

2017 ◽  
Vol 70 (12) ◽  
pp. 1247 ◽  
Author(s):  
Manjinder Kour ◽  
Raakhi Gupta ◽  
Raj K. Bansal
Keyword(s):  
Maleic Anhydride ◽  
Carbonyl Group ◽  
Carbonyl Compounds ◽  
Secondary Amines ◽  
Kinetic Control ◽  
Thermodynamic Control ◽  
Carbonyl Carbon ◽  
Fukui Functions ◽  
Unsaturated Carbonyl Compound ◽  
Condensed Fukui Functions

The reaction of secondary amines, namely 1-methylpiperazine, pyrrolidine, morpholine, 2-methylpiperidine, and diethylamine, with maleic anhydride has been investigated experimentally and theoretically at the DFT level. Under kinetic control, i.e. at −78°C or −15°C, amines add across the C=O functionality exclusively and the initially formed addition products isomerize to the corresponding N-substituted maleimic acid derivatives. In contrast to the acyclic α,β-unsaturated carbonyl compounds, amine does not add across the C=C functionality in maleic anhydride even under thermodynamic control. This behaviour of maleic anhydride can be rationalized on the basis of the local condensed Fukui functions, which reveal that the carbonyl carbon atoms in maleic anhydride are much harder than in an acyclic α,β-unsaturated carbonyl compound, such as acrolein. This prompts the amines to attack the carbonyl group in maleic anhydride exclusively.

scholarly journals Teaching a neural network to attach and detach electrons from molecules

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Roman Zubatyuk ◽  
Justin S. Smith ◽  
Benjamin T. Nebgen ◽  
Sergei Tretiak ◽  
Olexandr Isayev
Keyword(s):  
Machine Learning ◽  
Density Functional ◽  
Chemical Reactivity ◽  
Closed Shell ◽  
Machine Learning Algorithms ◽  
Electrophilic Aromatic Substitution ◽  
Interatomic Potentials ◽  
Aromatic Substitution ◽  
Conceptual Density Functional Theory ◽  
Fukui Functions

AbstractInteratomic potentials derived with Machine Learning algorithms such as Deep-Neural Networks (DNNs), achieve the accuracy of high-fidelity quantum mechanical (QM) methods in areas traditionally dominated by empirical force fields and allow performing massive simulations. Most DNN potentials were parametrized for neutral molecules or closed-shell ions due to architectural limitations. In this work, we propose an improved machine learning framework for simulating open-shell anions and cations. We introduce the AIMNet-NSE (Neural Spin Equilibration) architecture, which can predict molecular energies for an arbitrary combination of molecular charge and spin multiplicity with errors of about 2–3 kcal/mol and spin-charges with error errors ~0.01e for small and medium-sized organic molecules, compared to the reference QM simulations. The AIMNet-NSE model allows to fully bypass QM calculations and derive the ionization potential, electron affinity, and conceptual Density Functional Theory quantities like electronegativity, hardness, and condensed Fukui functions. We show that these descriptors, along with learned atomic representations, could be used to model chemical reactivity through an example of regioselectivity in electrophilic aromatic substitution reactions.

Revisiting the calculation of condensed Fukui functions using the quantum theory of atoms in molecules

2007 ◽  
Vol 126 (23) ◽  
pp. 234108 ◽  
Author(s):  
Nicolás Otero ◽  
Marcos Mandado ◽  
Ricardo A. Mosquera
Keyword(s):  
Quantum Theory ◽  
Atoms In Molecules ◽  
Fukui Functions ◽  
Condensed Fukui Functions

scholarly journals Critical thoughts on computing atom condensed Fukui functions

2007 ◽  
Vol 127 (3) ◽  
pp. 034102 ◽  
Author(s):  
Patrick Bultinck ◽  
Stijn Fias ◽  
Christian Van Alsenoy ◽  
Paul W. Ayers ◽  
Ramon Carbó-Dorca
Keyword(s):  
Fukui Functions ◽  
Condensed Fukui Functions

Quantification of reactive sites in DNA bases using condensed Fukui functions

2001 ◽  
Vol 544 (1-3) ◽  
pp. 123-139 ◽  
Author(s):  
D Sivanesan ◽  
V Subramanian ◽  
B Unni Nair
Keyword(s):  
Dna Bases ◽  
Fukui Functions ◽  
Condensed Fukui Functions

scholarly journals A DFT study of the chemical reactivity of thiobencarb and its oxidized derivatives in aqueous phase

2018 ◽  
Vol 83 (9) ◽  
pp. 981-993
Author(s):  
Luis Mendoza-Huizar
Keyword(s):  
Free Radical ◽  
Aromatic Ring ◽  
Aqueous Phase ◽  
Chemical Reactivity ◽  
Dft Study ◽  
Fukui Functions ◽  
Local Reactivity ◽  
Reactive Zone ◽  
Global And Local ◽  
Condensed Fukui Functions

In the present work, the global and local reactivity of S-(4-chlorobenzyl)- N,N-diethylthiocarbamate (TB) and its oxidized derivatives (sulfone (TBSu) and sulfoxide (TBS) were analyzed. In addition, the chemical reactivities of the dechlorinated forms of TB (DTB), TBSu (DTBSu) and TBS (DTBS) were studied. The calculations were performed at the wB97XD/6- -311++G(2d,2p) level of theory in the aqueous phase. The condensed Fukui functions indicated that for TB and DTB, the most preferred sites for donating electron in a reaction are located on the S and N atoms, while the most reactive sites for accepting electrons are associated with the aromatic ring (AR). For TBS and DTBS, the more reactive sites are located on AR, S and AR for nucleophilic, electrophilic and free radical attacks, respectively. In the case of TBSu and DTBSu, the results showed AR to be the more reactive zone for the three kinds of attacks. These last results suggest that cleavage of the C?S bond in TB, TBS and their dechlorinated forms is favored by electrophilic attacks. Additionally, the obtained results suggest that in TB, it is plausible that the cleavage of the C?N is favored on attack of this molecule by electrophiles.

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