molecules-logo

Journal Browser

Journal Browser

Special Issue "Modern Computational Methods for Chemical Bonding and Reactivity"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Computational and Theoretical Chemistry".

Deadline for manuscript submissions: closed (31 December 2019).

Special Issue Editors

Dr. Diego Andrada
E-Mail Website
Guest Editor
Krupp-Chair of General and Inorganic Chemistry, Saarland University, Campus, C4.1, 66123 Saarbrücken, Germany
Interests: DFT; chemical bonding; reactivity; main group chemistry; organometallic chemistry; inorganic chemistry
Prof. Dr. Israel Fernández
E-Mail Website
Guest Editor
Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Interests: reactivity; bonding situation; aromaticity; density functional theory; reaction mechanisms; organometallic chemistry

Special Issue Information

Dear Colleagues,

In the last decades, quantum chemical calculations have become a powerful tool to explain different aspects of chemistry. Several models of chemical bonds have been developed aiming at understanding and thus predicting molecular structures and chemical reactivity. Covalent bonds, donor–acceptor interactions, conjugation, hyperconjugation, aromaticity, and intermolecular interactions, among others, are well-established concepts that are used to explain the electronic properties and hence the reactivity. In this regard, deep understanding has been gained on a broad variety of systems, with the two different but complementary approaches used to analyze, quantify and rationalize the fundamental effects of chemical transformations. On the one hand, the molecular orbital-based methods—such as natural bond orbitals (NBO), energy decomposition analysis (EDA), and dispersion interaction densities (DID)—have been used to explain stability and chemical reactivity through the modern distortion/interaction–activation strain model. On the other hand, the topological-based methods—such as the quantum theory of atoms in molecules (QTAIM), the electron localization function (ELF), and the non-covalent interactions (NCIs)—have provided interesting insights through the interactive quantum atoms (IQA) theory, the bonding evolution theory, and the recently suggested molecular electron density theory (MEDT).

This Special Issue “Modern Computational Methods for Chemical Bonding and Reactivity” aims at gathering works on these two different approaches—molecular orbital-based and topological-based methods—to tackle the description of chemical bonding and reactivity in organic, inorganic and organometallic systems. Research papers, reviews or perspectives are welcome.

Dr. Diego Andrada
Prof. Dr. Israel Fernández López
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • chemical bond
  • conjugation
  • hyperconjugation
  • aromaticity
  • weak interactions
  • non covalent interactions
  • dispersion interactions
  • chemical reactivity
  • reaction mechanism
  • frontier molecular orbitals
  • quantum theory of atoms in molecules
  • electron localization function

Published Papers (4 papers)

Order results
Result details
Select all
Export citation of selected articles as:

Research

Open AccessArticle
How do the Hückel and Baird Rules Fade away in Annulenes?
Molecules 2020, 25(3), 711; https://doi.org/10.3390/molecules25030711 - 07 Feb 2020
Cited by 8 | Viewed by 977
Abstract
Two of the most popular rules to characterize the aromaticity of molecules are those due to Hückel and Baird, which govern the aromaticity of singlet and triplet states. In this work, we study how these rules fade away as the ring structure increases [...] Read more.
Two of the most popular rules to characterize the aromaticity of molecules are those due to Hückel and Baird, which govern the aromaticity of singlet and triplet states. In this work, we study how these rules fade away as the ring structure increases and an optimal overlap between p orbitals is no longer possible due to geometrical restrictions. To this end, we study the lowest-lying singlet and triplet states of neutral annulenes with an even number of carbon atoms between four and eighteen. First of all, we analyze these rules from the Hückel molecular orbital method and, afterwards, we perform a geometry optimization of the annulenes with several density functional approximations in order to analyze the effect that the distortions from planarity produce on the aromaticity of annulenes. Finally, we analyze the performance of three density functional approximations that employ different percentages of Hartree-Fock exchange (B3LYP, CAM-B3LYP and M06-2X) and Hartree-Fock. Our results reveal that functionals with a low percentage of Hartree-Fock exchange at long ranges suffer from severe delocalization errors that result in wrong geometrical structures and the overestimation of the aromatic character of annulenes. Full article
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
Show Figures

Graphical abstract

Open AccessArticle
Revisiting the Rearrangement of Dewar Thiophenes
Molecules 2020, 25(2), 284; https://doi.org/10.3390/molecules25020284 - 10 Jan 2020
Cited by 4 | Viewed by 1118
Abstract
The mechanism for the walk rearrangement in Dewar thiophenes has been clarified theoretically by studying the evolution of chemical bonds along the intrinsic reaction coordinates. Substituent effects on the overall mechanism are assessed by using combinations of the ring (R = H, CF [...] Read more.
The mechanism for the walk rearrangement in Dewar thiophenes has been clarified theoretically by studying the evolution of chemical bonds along the intrinsic reaction coordinates. Substituent effects on the overall mechanism are assessed by using combinations of the ring (R = H, CF3) and traveling (X = S, S = O, and CH2) groups. The origins of fluxionality in the S–oxide of perfluorotetramethyl Dewar thiophene are uncovered in this work. Dewar rearrangements are chemical processes that occur with a high degree of synchronicity. These changes are directly related to the activation energy. Full article
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
Show Figures

Graphical abstract

Open AccessArticle
Can We Safely Obtain Formal Oxidation States from Centroids of Localized Orbitals?
Molecules 2020, 25(1), 234; https://doi.org/10.3390/molecules25010234 - 06 Jan 2020
Cited by 2 | Viewed by 1647
Abstract
The use of centroids of localized orbitals as a method to derive oxidation states (OS) from first-principles is critically analyzed. We explore the performance of the closest-atom distance criterion to assign electrons for a number of challenging systems, including high-valent transition metal compounds, [...] Read more.
The use of centroids of localized orbitals as a method to derive oxidation states (OS) from first-principles is critically analyzed. We explore the performance of the closest-atom distance criterion to assign electrons for a number of challenging systems, including high-valent transition metal compounds, π-adducts, and transition metal (TM) carbenes. Here, we also introduce a mixed approach that combines the position of the centroids with Bader’s atomic basins as an alternative criterion for electron assignment. The closest-atom criterion performs reasonably well for the challenging systems, but wrongly considers O-H and N-H bonds as hydrides. The new criterion fixes this problem, but underperforms in the case of TM carbenes. Moreover, the OS assignment in dubious cases exhibit undesirable dependence on the particular choice for orbital localization. Full article
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
Show Figures

Graphical abstract

Open AccessArticle
On the Use of Popular Basis Sets: Impact of the Intramolecular Basis Set Superposition Error
Molecules 2019, 24(20), 3810; https://doi.org/10.3390/molecules24203810 - 22 Oct 2019
Cited by 4 | Viewed by 885
Abstract
The magnitude of intramolecular basis set superposition error (BSSE) is revealed via computing systematic trends in molecular properties. This type of error is largely neglected in the study of the chemical properties of small molecules and it has historically been analyzed just in [...] Read more.
The magnitude of intramolecular basis set superposition error (BSSE) is revealed via computing systematic trends in molecular properties. This type of error is largely neglected in the study of the chemical properties of small molecules and it has historically been analyzed just in the study of large molecules and processes dominated by non-covalent interactions (typically dimerization or molecular complexation and recognition events). In this work we try to provide proof of the broader prevalence of this error, which permeates all types of electronic structure calculations, particularly when employing insufficiently large basis sets. Full article
(This article belongs to the Special Issue Modern Computational Methods for Chemical Bonding and Reactivity)
Show Figures

Figure 1

Back to TopTop