Towards understanding proton affinity and gas-phase basicity with density functional reactivity theory

Huang, Ying; Liu, Lianghong; Liu, Shubin

doi:10.1016/j.cplett.2012.01.014

Cited by 31 publications

(24 citation statements)

References 19 publications

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“…They suggested that the more negative the MEP value, the stronger the molecular basicity, the larger the proton affinity and gas-phase basicity. Also they proposed that for systems with multiple sites of the same basic element type, the most basic site (largest energy decrease) has the most negative MEP value (Yuang et al, 2013). The numerical values of the MEP on the nuclei of basic centers and the valence natural atomic orbital energies of these centers for all species investigated here are also listed in Table 3.…”

Section: De Dh Dgmentioning

confidence: 97%

“…Yuang et al proposed a theoretical model to calculate this quantum descriptor can be found in Ref. (Yuang et al, 2013). They suggested that the more negative the MEP value, the stronger the molecular basicity, the larger the proton affinity and gas-phase basicity.…”

Section: De Dh Dgmentioning

confidence: 98%

“…It was pointed out that the molecular electrostatic potential (MEP) on the nuclei of a molecule originally invoked to study electrophilic reactivity (Yuang et al, 2013). The MEP of a molecule is a real physical property, and it can be determined experimentally by X-ray diffraction techniques (Suresh, 2006).…”

Section: De Dh Dgmentioning

confidence: 99%

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A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Safi

2016

Arabian Journal of Chemistry

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The results of a detailed DFT (B3LYP) investigation on five tautomers of thiazolidine-2,4-dione and their 5-substituted derivatives (ACH 3 , ANH 2 , ACl, AF, ACN-and NO 2 ) are presented here. The energy, geometrical parameters, topological parameters of all species in the gas phase have been calculated at B3LYP6-311++G(3df,2p)//B3LYP/311 + G(d,p) level of theory. The proton affinities (Pas), molecular electrostatic potential (MEP), natural valence atomic orbital energies (NNAO) of the basic center exist in the title compound in the gas phase have been calculated at the same level of theory. The specific hydration of the title compound by one water molecule has been also investigated at the same level of theory. Among the thiazolidine-2,4-dione tautomers and its derivatives, the most stable tautomer corresponds to the diketo forms (A), regardless of the substituent type. Results reveal that the oxygen atom of the carbonyl group at position 2 is more basic than the one at position 4. The existence of different hydrogen bond donor and acceptor centers in these molecules led to different kinds of intermolecular hydrogen bonds (CHAEAEAEO, NAHAEAEAEO and C‚OAEAEAEH) and different kinds of complexes. The stability of the cyclic complexes has been investigated using the analysis of Natural Bond Orbital (NBO), Atoms In Molecules topology, and the thermodynamic data. Results suggest that the water molecule prefers to bind with the oxygen atom, which has low intrinsic character. ª 2015 The Author. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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Section: De Dh Dgmentioning

confidence: 97%

Section: De Dh Dgmentioning

confidence: 98%

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A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Safi

2016

Arabian Journal of Chemistry

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“…Nevertheless, quantitative determination of these intrinsic physiochemical properties from theory and computation is still challenging. We previously proposed to use two equivalent descriptors, MEP (molecular electrostatic potential) and NAO (natural atomic orbital), for the purpose . Our more recent studies using ITA quantities indicated that better results could be obtained.…”

Section: Recent Applicationsmentioning

confidence: 99%

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Rong

Wang

Zhao

et al. 2019

WIREs Comput Mol Sci

Self Cite

106

116

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Using simple functionals of the electron density to appreciate and quantify molecular structure and chemical reactivity properties is a recent endeavor in density functional theory (DFT) toward the development of a new chemical reactivity theory. According to the first Hohenberg–Kohn theorem in DFT, the electron density alone should be able to determine any property in the ground state. Exchange and correlation energies are such properties, so are molecular structure and chemical reactivity, and hence they all should accurately be determined by electron density functionals. Quantities such as Shannon entropy, Fisher information, Ghosh–Berkowitz–Parr entropy, information gain, Onicescu information energy, etc., from the information‐theoretic approach are simple electron density functionals, whose analytical forms are exactly known. In this article, we demonstrate their usefulness and validity to quantify regioselectivity, stereoselectivity, and other structure and reactivity properties. We will outline the current understanding of its theoretical framework at first, and then highlight recent applications to chemical problems including isomeric and conformational stability, electrophilicity and nucleophilicity, strong covalent and weak noncovalent interactions, acidity and basicity, aromaticity and antiaromaticity, and numerous other properties. The effort of employing electron density functionals to quantify chemical concepts should open up a new door for us to ultimately develop a chemical reactivity theory using the DFT language. This article is characterized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory Structure and Mechanism > Molecular Structures Molecular and Statistical Mechanics > Molecular Interactions

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“…Available data of gas-phase proton affinities predict the favorable protonation site in the terpendoles. Proton affinities of indole and alkyl ketone were reported to be 891-986 kJ/mol [16][17][18][19] and up to 864 kJ/mol, [18] respectively. Their comparable proton affinities in paxilline (6) could cause the competitive proton localization between the ring A-C portion and the ring D-F portion with a ketone.…”

Section: Dear Sirmentioning

confidence: 99%

Detection of oxygen addition peaks for terpendole E and related indole-diterpene alkaloids in a positive-mode ESI-MS

et al. 2014

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This report describes that a regular positive electrospray ionization mass spectrometry (MS) analysis of terpendoles often causes unexpected oxygen additions to form [M + H + O]+ and [M + H + 2O]+, which might be a troublesome in the characterization of new natural analogues. The intensities of [M + H + O]+ and [M + H + 2O]+ among terpendoles were unpredictable and fluctuated largely. Simple electrochemical oxidation in electrospray ionization was insufficient to explain the phenomenon. So we studied factors to form [M + H + O]+ and [M + H + 2O]+ using terpendole E and natural terpendoles together with some model indole alkaloids. Similar oxygen addition was observed for 1,2,3,4-tetrahydrocyclopent[b]indole, which is corresponding to the substructure of terpendole E. In tandem MS experiments, a major fragment ion at m/z 130 from protonated terpendole E was assigned to the substructure containing indole. When the [M + H + O]+ was selected as a precursor ion, the ion shifted to m/z 146. The same 16 Da shift of fragments was also observed for 1,2,3,4-tetrahydrocyclopent[b]indole, indicating that the oxygen addition of terpendole E took place at the indole portion. However, the oxygen addition was absent for some terpendoles, even whose structure resembles terpendole E. The breakdown curves characterized the tandem MS features of terpendoles. Preferential dissociation into m/z 130 suggested the protonation tendency at the indole site. Terpendoles that are preferentially protonated at indole tend to form oxygen addition peaks, suggesting that the protonation feature contributes to the oxygen additions in some degrees. © 2014 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.

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Towards understanding proton affinity and gas-phase basicity with density functional reactivity theory

Cited by 31 publications

References 19 publications

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

A theoretical study on the structure of thiazolidine-2,4-dione and its 5-substituted derivatives in the gas phase. Implications for the thiazolidine-2,4-dione -water complex

Information‐theoretic approach in density functional theory and its recent applications to chemical problems

Detection of oxygen addition peaks for terpendole E and related indole-diterpene alkaloids in a positive-mode ESI-MS

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