Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
7.4
4.2
Journals
Molecules
Special Issues
Advances in the Theory of Chemical Bonding
molecules-logo
Submit to Molecules Review for Molecules Propose a Special Issue

Journal Menu

► Journal Menu

Journal Browser

► Journal Browser
share announcement

Advances in the Theory of Chemical Bonding

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

Deadline for manuscript submissions: closed (31 July 2021) | Viewed by 27880

Special Issue Editor

Prof. Dr. Ángel Martín Pendás

E-Mail Website
Guest Editor
Departamento de Química Física y Analítica, Julián Clavería, 6, Facultad de Química, Universidad de Oviedo, Oviedo, Spain
Interests: chemical bonding theory; quantum chemical topology; simulation of materials; matter at high pressure; methods in theoretical chemistry

Special Issue Information

Dear Colleagues,

It has been over a hundred years now since the seminal paper by G. N. Lewis was published in 1916, and many of the fundamental questions regarding the nature chemical bonds are still a subject of debate. We have recently witnessed, for instance, how purportedly well-established concepts like the steric nature of simple rotation barriers or the multiple-bonded character of naïve diatomics have been questioned with new interpretive tools. A literature survey also shows that as new fields become of interest, e.g., noncovalent interactions, heavily correlated systems, the chemistry of actinides, etc., the chemical bonding paradigm that works well in main-group elements loses power. Interestingly, the renaissance of long-time unattended methods, like valence bond theory, that carries an intrinsic interpretive toolbox, has also uncovered noteworthy disagreements with the traditional molecular pictures, and calls for new methods in the theory of chemical bonding based on orbital invariant descriptors.

It is, thus, a suitable time to gather experts across the different disciplines related to chemical bonding theory to showcase how the advent of new methods and the need to cope with unexplored bonding regimes is reshaping the field. Original research papers as well as reviews are welcome on new methodologies in orbital or real space, descriptors to cope with weakly bounded systems or with the spin structure of molecules, advances in conceptual density functional theory or the statistical distribution of electrons, energy decomposition schemes, etc. Applications of any of these methodologies to controversial cases or to bonding regimes far from the canon are particularly welcome, as are works comparing several possibly conflicting methodologies in a set of common systems.

Prof. Dr. Ángel Martín Pendás
Guest Editor

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 submissions that pass pre-check are 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 2700 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

  • theory of chemical bonding
  • energy decompositions
  • real space partitions
  • conceptual density functional theory
  • theoretical and computational chemistry
  • noncovalent interactions

Benefits of Publishing in a Special Issue

  • Ease of navigation: Grouping papers by topic helps scholars navigate broad scope journals more efficiently.
  • Greater discoverability: Special Issues support the reach and impact of scientific research. Articles in Special Issues are more discoverable and cited more frequently.
  • Expansion of research network: Special Issues facilitate connections among authors, fostering scientific collaborations.
  • External promotion: Articles in Special Issues are often promoted through the journal's social media, increasing their visibility.
  • e-Book format: Special Issues with more than 10 articles can be published as dedicated e-books, ensuring wide and rapid dissemination.

Further information on MDPI's Special Issue polices can be found here.

Published Papers (7 papers)

Download All Papers
Order results
Result details
Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:

Research

12 pages, 2233 KiB  
Article
Dual XH–π Interaction of Hexafluoroisopropanol with Arenes
by Le Lu and Ruimao Hua
Molecules 2021, 26(15), 4558; https://doi.org/10.3390/molecules26154558 - 28 Jul 2021
Cited by 10 | Viewed by 3312
Abstract
The dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/benzene complex (−7.22 kcal/mol) and the [...] Read more.
The dual XH (OH and CH) hydrogen-bond-donating property of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and the strong dual XH–π interaction with arenes were firstly disclosed by theoretical studies. Here, the high accuracy post-Hartree–Fock methods, CCSD(T)/CBS, reveal the interaction energy of HFIP/benzene complex (−7.22 kcal/mol) and the contribution of the electronic correlation energy in the total interaction energy. Strong orbital interaction between HFIP and benzene was found by using the DFT method in this work to disclose the dual XH–π intermolecular orbital interaction of HFIP with benzene-forming bonding and antibonding orbitals resulting from the orbital symmetry of HFIP. The density of states and charge decomposition analyses were used to investigate the orbital interactions. Isopropanol (IP), an analogue of HFIP, and chloroform (CHCl3) were studied to compare them with the classical OH–π, and non-classical CH–π interactions. In addition, the influence of the aggregating effect of HFIP, and the numbers of substituted methyl groups in benzene rings were also studied. The interaction energies of HFIP with the selected 24 common organic compounds were calculated to understand the role of HFIP as solvent or additive in organic transformation in a more detailed manner. A single-crystal X-ray diffraction study of hexafluoroisopropyl benzoate further disclosed and confirmed that the CH of HFIP shows the non-classical hydrogen-bond-donating behavior. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Graphical abstract

24 pages, 805 KiB  
Article
Exceptionally Long Covalent CC Bonds—A Local Vibrational Mode Study
by Alexis Antoinette Ann Delgado, Alan Humason, Robert Kalescky, Marek Freindorf and Elfi Kraka
Molecules 2021, 26(4), 950; https://doi.org/10.3390/molecules26040950 - 11 Feb 2021
Cited by 27 | Viewed by 4794
Abstract
For decades one has strived to synthesize a compound with the longest covalent C−C bond applying predominantly steric hindrance and/or strain to achieve this goal. On the other hand electronic effects have been added to the repertoire, such as realized in the electron [...] Read more.
For decades one has strived to synthesize a compound with the longest covalent C−C bond applying predominantly steric hindrance and/or strain to achieve this goal. On the other hand electronic effects have been added to the repertoire, such as realized in the electron deficient ethane radical cation in its D3d form. Recently, negative hyperconjugation effects occurring in diamino-o-carborane analogs such as di-N,N-dimethylamino-o-carborane have been held responsible for their long C−C bonds. In this work we systematically analyzed CC bonding in a diverse set of 53 molecules including clamped bonds, highly sterically strained complexes such as diamondoid dimers, electron deficient species, and di-N,N-dimethylamino-o-carborane to cover the whole spectrum of possibilities for elongating a covalent C−C bond to the limit. As a quantitative intrinsic bond strength measure, we utilized local vibrational CC stretching force constants ka(CC) and related bond strength orders BSO n(CC), computed at the ωB97X-D/aug-cc-pVTZ level of theory. Our systematic study quantifies for the first time that whereas steric hindrance and/or strain definitely elongate a C−C bond, electronic effects can lead to even longer and weaker C−C bonds. Within our set of molecules the electron deficient ethane radical cation, in D3d symmetry, acquires the longest C−C bond with a length of 1.935 Å followed by di-N,N-dimethylamino-o-carborane with a bond length of 1.930 Å. However, the C−C bond in di-N,N-dimethylamino-o-carborane is the weakest with a BSO n value of 0.209 compared to 0.286 for the ethane radical cation; another example that the longer bond is not always the weaker bond. Based on our findings we provide new guidelines for the general characterization of CC bonds based on local vibrational CC stretching force constants and for future design of compounds with long C−C bonds. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Graphical abstract

21 pages, 4418 KiB  
Article
Ab Initio Dot Structures Beyond the Lewis Picture
by Michael A. Heuer, Leonard Reuter and Arne Lüchow
Molecules 2021, 26(4), 911; https://doi.org/10.3390/molecules26040911 - 9 Feb 2021
Cited by 6 | Viewed by 2475
Abstract
The empirical Lewis picture of the chemical bond dominates the view chemists have of molecules, of their stability and reactivity. Within the mathematical framework of quantum mechanics, all this chemical information is hidden in the many-particle wave function Ψ. Thus, to reveal [...] Read more.
The empirical Lewis picture of the chemical bond dominates the view chemists have of molecules, of their stability and reactivity. Within the mathematical framework of quantum mechanics, all this chemical information is hidden in the many-particle wave function Ψ. Thus, to reveal and understand it, there is great interest in enhancing the Lewis model and connecting it to computable quantities. As has previously been shown, the Lewis picture can often be recovered from the probability density |Ψ|2 with probabilities in agreement with valence bond weights: the structures appear as most likely positions in the all-electron configuration space. Here, we systematically expand this topological probability density analysis to molecules with multiple bonds and lone pairs, employing correlated Slater-Jastrow wave functions. In contrast to earlier studies, non-Lewis structures are obtained that disagree with the prevalent picture and have a potentially better predictive capability. While functional groups are still recovered with these ab initio structures, the boundary between bonds and lone pairs is mostly blurred or non-existent. In order to understand the newly found structures, the Lewis electron pairs are replaced with spin-coupled electron motifs as the fundamental electronic fragment. These electron motifs—which coincide with Lewis’ electron pairs for many single bonds—arise naturally from the generally applicable analysis presented. An attempt is made to rationalize the geometry of the newly-found structures by considering the Coulomb force and the Pauli repulsion. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Graphical abstract

16 pages, 2727 KiB  
Article
Energetics of Electron Pairs in Electrophilic Aromatic Substitutions
by Julen Munárriz, Miguel Gallegos, Julia Contreras-García and Ángel Martín Pendás
Molecules 2021, 26(2), 513; https://doi.org/10.3390/molecules26020513 - 19 Jan 2021
Cited by 4 | Viewed by 3453
Abstract
The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown [...] Read more.
The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Graphical abstract

19 pages, 3136 KiB  
Article
NBO/NRT Two-State Theory of Bond-Shift Spectral Excitation
by Yinchun Jiao and Frank Weinhold
Molecules 2020, 25(18), 4052; https://doi.org/10.3390/molecules25184052 - 4 Sep 2020
Cited by 9 | Viewed by 3437
Abstract
We show that natural bond orbital (NBO) and natural resonance theory (NRT) analysis methods provide both optimized Lewis-structural bonding descriptors for ground-state electronic properties as well as suitable building blocks for idealized “diabatic” two-state models of the associated spectroscopic excitations. Specifically, in the [...] Read more.
We show that natural bond orbital (NBO) and natural resonance theory (NRT) analysis methods provide both optimized Lewis-structural bonding descriptors for ground-state electronic properties as well as suitable building blocks for idealized “diabatic” two-state models of the associated spectroscopic excitations. Specifically, in the framework of single-determinant Hartree-Fock or density functional methods for a resonance-stabilized molecule or supramolecular complex, we employ NBO/NRT descriptors of the ground-state determinant to develop a qualitative picture of the associated charge-transfer excitation that dominates the valence region of the electronic spectrum. We illustrate the procedure for the elementary bond shifts of SN2-type halide exchange reaction as well as the more complex bond shifts in a series of conjugated cyanine dyes. In each case, we show how NBO-based descriptors of resonance-type 3-center, 4-electron (3c/4e) interactions provide simple estimates of spectroscopic excitation energy, bond orders, and other vibronic details of the excited-state PES that anticipate important features of the full multi-configuration description. The deep 3c/4e connections to measurable spectral properties also provide evidence for NBO-based estimates of ground-state donor-acceptor stabilization energies (sometimes criticized as “too large” compared to alternative analysis methods) that are also found to be of proper magnitude to provide useful estimates of excitation energies and structure-dependent spectral shifts. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Graphical abstract

26 pages, 3812 KiB  
Article
Spin Density Topology
by Giovanna Bruno, Giovanni Macetti, Leonardo Lo Presti and Carlo Gatti
Molecules 2020, 25(15), 3537; https://doi.org/10.3390/molecules25153537 - 2 Aug 2020
Cited by 26 | Viewed by 5325
Abstract
Despite its role in spin density functional theory and it being the basic observable for describing and understanding magnetic phenomena, few studies have appeared on the electron spin density subtleties thus far. A systematic full topological analysis of this function is lacking, seemingly [...] Read more.
Despite its role in spin density functional theory and it being the basic observable for describing and understanding magnetic phenomena, few studies have appeared on the electron spin density subtleties thus far. A systematic full topological analysis of this function is lacking, seemingly in contrast to the blossoming in the last 20 years of many studies on the topological features of other scalar fields of chemical interest. We aim to fill this gap by unveiling the kind of information hidden in the spin density distribution that only its topology can disclose. The significance of the spin density critical points, the 18 different ways in which they can be realized and the peculiar topological constraints on their number and kind, arising from the presence of positive and negative spin density regions, is addressed. The notion of molecular spin graphs, spin maxima (minima) joining paths, spin basins and of their valence is introduced. We show that two kinds of structures are associated with a spin–polarized molecule: the usual one, defined through the electron density gradient, and the magnetic structure, defined through the spin density gradient and composed in general by at least two independent spin graphs, related to spin density maxima and minima. Several descriptors, such as the spin polarization index, are introduced to characterize the properties of spin density critical points and basins. The study on the general features of the spin density topology is followed by the specific example of the water molecule in the 3B1 triplet state, using spin density distributions of increasing accuracy. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Figure 1

12 pages, 2987 KiB  
Article
Equilibrium Bond Lengths from Orbital-Free Density Functional Theory
by Kati Finzel
Molecules 2020, 25(8), 1771; https://doi.org/10.3390/molecules25081771 - 13 Apr 2020
Cited by 9 | Viewed by 3874
Abstract
This work presents an investigation to model chemical bonding in various dimers based on the atomic fragment approach. The atomic fragment approach is an ab-initio, parameter-free implementation of orbital-free density functional theory which is based on the bifunctional formalism, i.e., it uses both [...] Read more.
This work presents an investigation to model chemical bonding in various dimers based on the atomic fragment approach. The atomic fragment approach is an ab-initio, parameter-free implementation of orbital-free density functional theory which is based on the bifunctional formalism, i.e., it uses both the density and the Pauli potential as two separate variables. While providing the exact Kohn-Sham Pauli kinetic energy when the orbital-based Kohn-Sham data are used, the bifunctional formalism allows for approximations of the functional derivative which are orbital-free. In its first implementation, the atomic fragment approach uses atoms in their ground state to model the Pauli potential. Here, it is tested how artificial closed-shell fragments with non-integer electron occupation perform regarding the prediction of bond lengths of diatomics. Such fragments can sometimes mimic the electronic structure of a molecule better than groundstate fragments. It is found that bond lengths may indeed be considerably improved in some of the tested diatomics, in accord with predictions based on the electronic structure. Full article
(This article belongs to the Special Issue Advances in the Theory of Chemical Bonding)
►▼ Show Figures

Figure 1

Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:
 
Displaying articles 1-7
Back to TopTop