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Explosion begins by rupture of a specific bond, in the explosive, called a trigger linkage. We characterize this bond in nitro-containing explosives. Valence-bond (VB) investigations of X-NO2 linkages in alkyl nitrates, nitramines, and nitro esters establish the existence of Pauli repulsion that destabilizes the covalent structure of these bonds. The trigger linkages are mainly stabilized by covalent-ionic resonance and are therefore charge-shift bonds (CSBs). The source of Pauli repulsion in nitro explosives is unique. It is traced to the hyperconjugative interaction from the oxygen lone pairs of NO2 into the σ(X-N)* orbital, which thereby weakens the X-NO2 bond, and depletes its electron density as X becomes more electronegative. Weaker trigger bonds have higher CSB characters. In turn, weaker bonds increase the sensitivity of the explosive to impacts/shocks which lead to detonation. Application of the analysis to realistic explosives supports the CSB character of their X-NO2 bonds by independent criteria. Furthermore, other families of explosives also involve CSBs as trigger linkages (O-O, N-O, Cl-O, N-I, etc. bonds). In all of these, detonation is initiated selectively at the CSB of the molecule. A connection is made between the CSB bond-weakening and the surface-electrostatic potential diagnosis in the trigger bonds.

This Perspective outlines a panoramic description of the nature of the chemical bond according to valence bond theory. It describes single bonds and demonstrates the existence of a “forgotten family” of charge-shift bonds (CSBs) in which the entire/most of the bond energy arises from the resonance between the covalent and ionic structures of the bond. Many of the CSBs are homonuclear bonds. Hypervalent molecules (e.g., XeF2) are CSBs. This Perspective proceeds to describe multiple bonded molecules with an emphasis on C2 and 3O2. C2 has four electron pairs in its valence shell and, hence, 14 covalent structures and 1750 ionic structures. This Perspective outlines an effective methodology of peeling the electronic structure to the minimal and important number of structures: a dominant structure that displays a quadruple bond and two minor structures with [Formula: see text] + [Formula: see text] bonds, which stabilize the quadruple bond by resonance. 3O2 is chosen because it is a diradical, which is persistent and life-sustaining. It is shown that the persistence of this diradical is due to the charge-shift bonding of the [Formula: see text]-3-electron bonds. This section ends with a discussion of the roles of [Formula: see text] vs [Formula: see text] in the geometric preferences of benzene, acetylene, ethene, and their Si-based analogs. Subsequently, this Perspective discusses bonding in clusters of univalent metal atoms, which possess only parallel spins (n+1Mn), and are nevertheless bonded due to the resonance interactions that stabilize the repulsive elementary structure (all spins are up). The bond energy reaches ∼40 kcal/mol for a pair of atoms (in n+1Cun; n ∼ 10–12). The final subsection discusses singlet excited states in ethene, ozone, and SO2. It demonstrates the capability of the breathing-orbital VB method to yield an accurate description of a variety of excited states using merely 10 or few VB structures. Furthermore, the method underscores covalent structures that play a key role in the correct description and bonding of these excited states.

Noncovalent interactions are ubiquitous and have been well recognized in chemistry, biology and material science. Yet, there are still recurring controversies over their natures, due to the wide range of noncovalent interaction terms. In this Essay, we employed the Valence Bond (VB) methods to address two types of interactions which recently have drawn intensive attention, i.e., the halogen bonding and the CH‧‧‧HC dihydrogen bonding. The VB methods have the advantage of interpreting molecular structures and properties in the term of electron-localized Lewis (resonance) states (structures), which thereby shed specific light on the alteration of the bonding patterns. Due to the electron localization nature of Lewis states, it is possible to define individually and measure both polarization and charge transfer effects which have different physical origins. We demonstrated that both the ab initio VB method and the block-localized wavefunction (BLW) method can provide consistent pictures for halogen bonding systems, where strong Lewis bases NH

We present here a general conceptualization of the nature of metal-metal (M-M) bonding in transition-metal (TM) complexes across the periods of TM elements, by use of ab initio valence-bond theory. The calculations reveal a dual-trend: For M-M bonds in groups 7 and 9, the 3d-series forms charge-shift bonds (CSB), while upon moving down to the 5d-series, the bonds become gradually covalent. In contrast, M-M bonds of metals having filled d-orbitals (groups 11 and 12) behave oppositely; initially the M-M bond is covalent, but upon moving down the Periodic Table, the CSB character increases. These trends originate in the radial-distribution-functions of the atomic orbitals, which determine the compactness of the valence-orbitals vis-a-vis the filled semicore orbitals. Key factors that gauge this compactness are the presence/absence of a radial-node in the valence-orbital and relativistic contraction/expansion of the valence/semicore orbitals. Whenever these orbital-types are spatially coincident, the covalent bond-pairing is weakened by Pauli-repulsion with the semicore electrons, and CSB takes over. Thus, for groups 3-10, which possess (n - 1)s2(n - 1)p6 semicores, this spatial-coincidence is maximal at the 3d-transition-metals which consequently form charge-shift M-M bonds. However, in groups 11 and 12, the relativistic effects maximize spatial-coincidence in the third series, wherein the 5d10 core approaches the valence 6s orbital, and the respective Pauli repulsion generates M-M bonds with CSB character. These considerations create a generalized paradigm for M-M bonding in the transition-elements periods, and Pauli repulsion emerges as the factor that unifies CSB over the periods of main-group and transition elements.

Introductory chemistry textbooks often present valence bond (VB) theory as useful, but incorrect and inferior to molecular orbital (MO) theory, citing the electronic structure of O2 and electron de...

Charge-shift bonds (CSBs) constitute a new class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures. This Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus, valence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as a variety of electron density theories all show the distinction of CSBs vis-a-vis covalent and ionic bonds. Furthermore, the covalent-ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules, e.g., benzene. The Essay ends by arguing that CSBs are a distinct family of bonding, with a potential to bring about a Renaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.

We present here a versatile computational code named "elecTric fIeld generaTion And maNipulation (TITAN)," capable of generating various types of external electric fields, as well as quantifying the local (or intrinsic) electric fields present in proteins and other biological systems according to Coulomb's Law. The generated electric fields can be coupled with quantum mechanics (QM), molecular mechanics (MM), QM/MM, and molecular dynamics calculations in most available software packages. The capabilities of the TITAN code are illustrated throughout the text with the help of examples. We end by presenting an application, in which the effects of the local electric field on the hydrogen transfer reaction in cytochrome P450 OleTJE enzyme and the modifications induced by the application of an oriented external electric field are examined. We find that the protein matrix in P450 OleTJE acts as a moderate catalyst and that orienting an external electric field along the Fe─O bond of compound I has the biggest impact on the reaction barrier. The induced catalysis/inhibition correlates with the calculated spin density on the O-atom. © 2019 Wiley Periodicals, Inc.

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre-ionized state. Therefore, these experiments do not lead to a "selection of the correct orbitals" in chemistry and do not overturn the well-known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.

This study investigates the rich mechanistic landscape of the iconic electrophilic aromatic substitution (EAS) reaction class, in the gas phase, in solvents, and under stimulation by oriented external electric fields. The study uses DFT calculations, complemented by a qualitative valence bond (VB) perspective. We construct a comprehensive and unifying framework that elucidates the many surprising mechanistic features, uncovered in recent years, of this class of reactions. For example, one of the puzzling issues which have attracted significant interest recently is the finding of a variety of concerted mechanisms that do not involve the formation of σ-complex intermediates, in apparent contradiction to the generally accepted textbook mechanism. Our VB modeling elucidates the existence of both the concerted and stepwise mechanisms and uncovers the root causes and necessary conditions for the appearance of these intermediates. Furthermore, our VB analysis offers insight into the potential applications of external electric fields as smart, green, and selective catalysts, which can control at will reaction rates, as well as mechanistic crossovers, for this class of reactions. Finally, we highlight how understanding of the electric fields effect on the EAS reaction could lead to the formulation of guiding principles for the design of improved heterogeneous catalysts. Overall, our analysis underscores the powerful synergy offered by combining molecular orbital and VB theory to tackle interesting and challenging mechanistic questions in chemistry.

This theoretical study establishes ways of controlling and enabling an uncommon chemical reaction, the displacement reaction, B:---(X—Y) → (B—X)+ + :Y–, which is nascent from a B:---(X—Y) halogen bond (XB) by nucleophilic attack of the base, B:, on the halogen, X. In most of the 14 cases examined, these reactions possess high barriers either in the gas phase (where the X—Y bond dissociates to radicals) or in solvents such as CH2Cl2 and CH3CN (which lead to endothermic processes). Thus, generally, the XB species are trapped in deep minima, and their reactions are not allowed without catalysis. However, when an oriented-external electric field (OEEF) is directed along the B---X---Y reaction axis, the field acts as electric tweezers that orient the XB along the field’s axis, and intensely catalyze the process, by tens of kcal/mol, thus rendering the reaction allowed. Flipping the OEEF along the reaction axis inhibits the reaction and weakens the interaction of the XB. Furthermore, at a critical OEEF, each XB...

This essay describes the successive births of valence bond (VB) theory during 1916–1931. The alternative molecular orbital (MO) theory was born in the late 1920s. The presence of two seemingly different descriptions of molecules by the two theories led to struggles between the main proponents, Linus Pauling and Robert Mulliken, and their supporters. Until the 1950s, VB theory was dominant, and then it was eclipsed by MO theory. The struggles will be discussed, as well as the new dawn of VB theory, and its future.

The manuscript studies the enantioselectivity and stereoselectivity of Diels-Alder (DA) cycloadditions between cyclopentadiene (CPD) and a variety of dienophiles (ranging from halo-ethenes to cyano-ethenes), under oriented external electric fields (OEEFs). Applying OEEFs oriented in the X/ Y directions, perpendicular to the reaction axis ( Z), will achieve complete isomeric and enantiomeric discrimination of the products. Unlike the Z-OEEF, which involves charge-transfer from the diene to the dienophile, and thereby brings about catalysis due to increased intramolecular bonding, an OEEF along X, aligned parallel to the C1-C4 atoms of CPD, will lead to R/ S enantiomeric discrimination by means of intramolecular-bond polarization. A Y field will discriminate endo/exo stereoisomers in a similar mechanism. The XY field-combination will resolve both R/S and endo/exo. The resolution is complete and can be achieved at will by flipping the direction of the field along the X and Y axes. The preconditions for achieving the enantiomeric and isomeric discrimination are discussed and require fixing of the CPD onto a surface. In so doing the chiral discrimination is achieved by dipole-moment selection rules, such that the field filters out one of the enantiomers, which is highly raised in energy by dipole selection. The dependence of the discrimination on the polarity of the dienophiles leads to a predictive trend.

Oriented external electric fields (OEEFs) are potent effectors of chemical change and control. We show that the Menshutkin reaction, between substituted pyridines and methyl iodide, can be catalyzed/inhibited at will, by just flipping the orientation of the EEF (FZ) along the “reaction axis” (Z), N---C---I. A theoretical analysis shows that catalysis/inhibition obey the Bell–Evans–Polanyi principle. Significant catalysis is predicted also for EEFs oriented off the reaction axis. Hence, the observation of catalysis can be scaled up and may not require orienting the reactants vis-a-vis the field. It is further predicted that EEFs can also catalyze the front-side nucleophilic displacement reaction, thus violating the Walden-inversion paradigm. Finally, we considered the impact of gold–thiolate linkers, used experimentally to deliver the EEF stimuli, on the Menshutkin reaction. A few linkers were tested and proved not to be innocent. In the presence of FZ, the linkers participate in the electronic reorganizat...

Recent theoretical studies suggested that hydrogen bonds between ions of like charges are of a covalent nature due to the dominating nD →σ*H-A charge-transfer (CT) interaction. In this work, energy profiles of typical hydrogen (H) and halogen (X) bonding systems formed from ions of like charges are explored using the block-localized wavefunction (BLW) method, which can derive optimal geometries and wave functions with the CT interaction "turned off." The results demonstrate that the kinetic stability, albeit reduced, is maintained for most investigated systems even after the intermolecular CT interaction is quenched. Further energy decomposition analyses based on the BLW method reveal that, despite a net repulsive Coulomb repulsion, a stabilizing component exists due to the polarization effect that plays significant role in the kinetic stability of all systems. Moreover, the fingerprints of the augmented electrostatic interaction due to polarization are apparent in the variation patterns of the electron density. All in all, much like in standard H- and X-bonds, the stability of such bonds between ions of like charges is governed by the competition between the stabilizing electrostatic and charge transfer interactions and the destabilizing deformation energy and Pauli exchange repulsion. While in most cases of "anti-electrostatic" bonds the CT interaction is of a secondary importance, we also find cases where CT is decisive. As such, this work validates the existence of anti-electrostatic H- and X-bonds. © 2017 Wiley Periodicals, Inc.

A general approach to hybridization, without imposing orthogonality of the hybrids of the central atom, is formulated. It is shown that the overlapping hybrids follow the rules of electronegativity of the central atom, and they increase with the increase of electronegativity (e.g. NH 4 + > CH 4 > BH 4 − ). For a given electronegativity, the hybrid-hybrid overlap decreases as the number of equivalent bonds increases (e.g., CH 4 3 + , CH 2 2+ ). Having the hybrid-hybrid overlap enables us to deduce the promotion energy invested by the various atoms to form the molecule; the larger the overlap the smaller the degree of hybridization, and the lesser is the promotion energy needed from the central atom to achieve maximum bonding. The approach is applied to the dicarbon molecule, C 2 . It is shown that after taking into account the promotion energy (∼46 kcal mol −1 per C), C 2 exhibits a quadruple bond.

The current usage of bond-length/bond-strength (BLBS) correlations, namely, that a shorter bond must be associated with larger dissociation energy and/or force constant, is appraised. The numerous exceptions to these rules are noted. The originators of these rules considered them as useful empirical correlations, but in the course of time these relationships have often been painted as laws. As shall be seen, each exception to these rules can be explained by some effects, like strain, steric effects, dispersion stabilization, hybridization defects, bond ionicity, orbital shrinkage, and so on. As such, when the number of special reasons that can be invoked for failures of the BLBS rules, is close to the number of the exceptions to these rules, one must conclude that such correlations cannot be considered as anything even close to physical laws. Indeed, it is often the exceptions to the rules that point to interesting bonding aspects and/or reorganization processes. We argue against disregarding bond dissociation energies or related energy quantities in this context. While the various reorganization processes involved in determining these energy quantities may complicate the BLBS correlations appreciably, compared to the properties that probe structures only close to equilibrium, their consideration cannot be avoided if we want to extract chemical sense from the notion of a bond strength.

The nature of the electronic-structure of polyenes, their delocalization features, and potential diradicaloid characters constitute a fundamental problem in chemistry. To address this problem, we used valence bond self-consistent field (VBSCF) calculations and modeling of polyenes, C2nH2n+2 (n = 2–10). The theoretical treatment shows that starting with n = 5, the polyene’s wave function is mainly a shifting 1,4-diradicaloid, a character that increases as the chain length increases, while the contribution of the fundamental Lewis structure with alternating double and single bonds (1) decays quite fast and becomes minor relative to the diradicaloid pack. We show how, nevertheless, it is this wave function that predicts that polyenes will still exhibit alternating short/long CC bonds like the fundamental structure 1. Furthermore, despite the decay of the VB contribution of 1, it remains the single structure with the largest weight among all the individual structures. The mixing of all the 1,4-diradicaloid st...

Polyhalogen monoanions [X2n+1 ]- (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X- non-classically bonded to a number of dihalogen molecules X2 via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X- and the σ-anti-bonding orbital of X2 molecule (n→σ*) in X3- and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X2n-1 ]- and X2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X2n+1 ]- . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X- and nX2 molecules exhibits the same trends as in X- with a single X2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X3 ]- anion. As such, the X- ⋅⋅⋅X2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X2n+1 ]- family.

In recent years, external electric fields (EEFs) have captured some spotlight as novel effectors of chemical change. EEFs directly impact the structure of molecular systems. For example, aligning an electric field along a specific bond-axis leads to either shortening or elongation of the bond (and ultimately bond breaking). Furthermore, EEFs enable unprecedented control over chemical reactivity. Orienting an electric field along the so-called “reaction-axis,” the direction in which the electrons reorganize during the conversion from reactant to product, leads to catalysis or inhibition and can induce mechanistic crossover from concerted to stepwise reactions. Off-reaction-axis orientation enables control over the stereoselectivity of reactions and disables forbidden–orbital mixing. Two-directional fields enable control over both reactivity and selectivity. In this advanced review, we offer an overview of this rapidly evolving research field with a focus on the valence bond modeling of EEF effects and the insight it offers. A wide variety of examples will be considered and a link to the experiment will be made throughout. We end by offering some perspectives in which we postulate that, as experimental techniques continue to mature, EEFs could potentially become a generally applicable “zapping” tool to facilitate elaborate chemical syntheses. This article is categorized under:. Structure and Mechanism > Reaction Mechanisms and Catalysis.

The present contribution uses a valence bond (VB) perspective to consider the captodative substitution strategy, a method to enhance the diradical character of (potentially aromatic) compounds. We confirm the qualitative reasoning that has generally been used to rationalize the diradical-character-enhancing effect of captodative substitution: this type of substitution scheme disproportionally stabilizes specific Dewar/diradical(oid) VB structures, thus increasing their weight in the full ground-state wave function. Furthermore, we assess the effect of captodative substitution on the aromaticity of the considered compound. We observe a clear trade-off between diradical character and aromaticity for our model systems: as one of these properties increases, the other decreases. This finding is especially significant within the field of single-molecule electronics because it enables unification of the previously observed inverse proportionality between the aromaticity of a compound and the magnitude of conductance through that molecule, with the observed proportionality between diradical character and the magnitude of conductance associated with a compound. To some extent, both properties, i.e., aromaticity and diradical character, appear to be the flip-sides of the same coin.

The authors of the above entitled paper suggest that molecular orbital (MO) and valence bond (VB) theories may generate conflicting insights into bonding. Therefore, they derive a real-space (RS) quantum chemical topology (QCT) approach (QCT-RS), and use it to extract insight into the H2 and LiH bonds, and contrast this insight with the one generated by VB calculations. The authors’ conclusions strongly contradict the usual bonding paradigms that arise from classical VB theory. Our Comment critically examines these claims and shows that MO and VB theories do not differ in their interpretations of bonding when both are applied on equal footing. It is furthermore shown that the conclusions based on this QCT-RS approach originate from a redefinition of VB structures in a manner that departs from the commonly accepted ones. This disparity of definitions of VB structures creates confusion. Thus, (a) the claim that in QCT-RS all covalency emanates from the covalent-ionic resonance, is generally incorrect in classical VB theory; and (b) contrary to the description of LiH as fully ionic in the above entitled paper, classical VB theory shows that this bond is well described as a superposition of a major covalent structure (albeit polarized) and a less important ionic one. The s–p hybridization of Li in the covalent structure is the major contributor to the dipole moment of LiH.

This study examined the nature of the electronic structure of representative cross-conjugated polyenes from a valence bond (VB) perspective. Our VBSCF calculations on a prototypical dendralene model reveal a remarkable inhibition of the delocalization compared to linear polyenes. Especially along the C-C backbone, the delocalization is virtually quenched so that these compounds can essentially be considered as sets of isolated butadiene units. In direct contrast to the dendralene chains, quinodimethane compounds exhibit an enhancement in their delocalization compared to linear polyenes. We demonstrate that this quenching/enhancement of the delocalization is inherently connected to the relative weights of specific types of long-bond VB structures. From our ab initio treatment, many localization/delocalization-related concepts and phenomena, central to both organic chemistry and single-molecule electronics, emerge. Not only do we find direct insight into the relation between topology and the occurrence of quantum interference (QI), but we also find a phenomenological justification of the recently proposed diradical character-based rule for the estimation of the magnitude of molecular conductance. Generally, our results can be conceptualized using the "arrow-pushing" concept, originating from resonance theory.

Few concepts are more familiar to chemists than the concept of acidity strength. In almost any undergraduate chemistry textbook, one can find lists of factors affecting the acidities of organic and inorganic molecules. The factors, invoked to explain trends in the acidity strength through series of compounds, rely on concepts such as hybridization, delocalization, inductive effects, and electronegativity. Some of these concepts could be considered somewhat fuzzy, whereas others have a rigorous physical definition, yet together they shape the traditional framework used by chemists for the qualitative assessment of acidity strengths. At the same time, a thermodynamic cycle reveals that the acidity of a H-A bond is dependent on only three unequivocally definable quantities: the bond dissociation energy, the electron affinity of A, and the solvent effects. Here we attempt to answer the following questions: "How are the qualitative factors, found in textbooks, related to these quantities?" and "How can we connect this plethora of factors to the nature of the acidic H-A bond being cleaved heterolytically in an acidic dissociation process?" To do so, we turn to valence bond theory and model a generic acidic dissociation process. Within this model, the quantities, determining the acidity strength of an H-A compound (as revealed through the thermodynamic cycling process), arise naturally and lucidly, thus enabling the evaluation of the effects of the different qualitative factors found in the literature on the bonding situation. Our analysis projects surprising and thought-provoking anomalies, which challenge common chemical knowledge.

Ever since Lewis depicted the triple bond for acetylene, triple bonding has been considered as the highest limit of multiple bonding for main elements. Here we show that C2 is bonded by a quadruple bond that can be distinctly characterized by valence-bond (VB) calculations. We demonstrate that the quadruply-bonded structure determines the key observables of the molecule, and accounts by itself for about 90% of the molecule's bond dissociation energy, and for its bond lengths and its force constant. The quadruply-bonded structure is made of two strong π bonds, one strong σ bond and a weaker fourth σ-type bond, the bond strength of which is estimated as 17-21 kcal mol(-1). Alternative VB structures with double bonds; either two π bonds or one π bond and one σ bond lie at 129.5 and 106.1 kcal mol(-1), respectively, above the quadruply-bonded structure, and they collapse to the latter structure given freedom to improve their double bonding by dative σ bonding. The usefulness of the quadruply-bonded model is underscored by "predicting" the properties of the (3)Σ+u state. C2's very high reactivity is rooted in its fourth weak bond. Thus, carbon and first-row main elements are open to quadruple bonding!

This is a tutorial on use of external-electric-fields (EEFs) as effectors of chemical change. The tutorial instructs readers how to conceptualize and design electric-field effects on bonds, structures, and reactions. Most effects can be comprehended as the field-induced stabilization of ionic structures. Thus, orienting the field along the “bond axis” will facilitate bond breaking. Similarly, orienting the field along the “reaction axis”, the direction in which “electron pairs transform” from reactants- to products-like, will catalyse the reaction. Flipping the field's orientation along the reaction-axis will cause inhibition. Orienting the field off-reaction-axis will control stereo-selectivity and remove forbidden-orbital mixing. Two-directional fields may control both reactivity and selectivity. Increasing the field strength for concerted reactions (e.g., Diels–Alder's) will cause mechanistic-switchover to stepwise mechanisms with ionic intermediates. Examples of bond breaking and control of reactivity/selectivity and mechanisms are presented and analysed from the “ionic perspective”. The tutorial projects the unity of EEF effects, “giving insight and numbers”.

Intermolecular attractive interaction between electrophilic sites is a counterintuitive phenomenon, as the electrostatic interaction therein is repulsive and destabilizing. Here, we confirm this phenomenon in four representative complexes, using state-of-the-art quantum mechanical methods. By employing the block-localized wavefunction (BLW) method, which can turn off intermolecular charge transfer interactions, we profoundly demonstrated the significance of charge transfer interactions in these seemingly counterintuitive complexes. Indeed, after being "turned off" the intermolecular charge transfer interaction in, for example, the FNSi···BrF complex, the originally attractive intermolecular interaction turns to be repulsive. The energy decomposition approach based on the BLW method (BLW-ED) can partition the overall stability gained on the formation of intermolecular noncovalent interaction into several physically meaningful components. According to the BLW-ED analysis, the electrostatic repulsion in these counterintuitive cases is overwhelmed by the stabilizing polarization, dispersion interaction, and most importantly, the charge transfer interaction, resulting in the eventual counterintuitive overall attraction. The present study suggests that, predicting bonding sites of noncovalent interactions using only the "hole" concept may be not universally sufficient, because other significant stabilizing factors will contribute to the stability and sometimes, play even bigger roles than the electrostatic interaction and consequently govern the complex structures. © 2018 Wiley Periodicals, Inc.

We analyze the properties of 15 3-electron bonds, which include σ-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, π-3-electron-bonds as in hydrazine radical cations, and doubly-π-(3e)-bonded species such as O2, FeO+, S2, etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RECS) of the three electrons, and the bond dissociation energies (De). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian (L) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such a...

We tell the story of the Lise Meitner-Minerva Center, its establishment and activities, its members and their scientific activity, and its instrumental role in weaving intense relationships with the theoretical community in Germany, and in amalgamating the Israeli community of computational quantum chemistry into a national center that enjoys a high international reputation.

The lowest excited state of the acetylenyl radical, HCC, is a 2Π state, only 0.46 eV above the ground state, 2Σ+. The promotion of an electron from a π bond pair to a singly occupied σ hybrid orbital is all that is involved, and so we set out to tune those orbital energies, and with them the relative energetics of 2Π and 2Σ+ states. A strategy of varying ligand electronegativity, employed in a previous study on substituted carbynes, RC, was useful, but proved more difficult to apply for substituted acetylenyl radicals, RCC. However, π-donor/acceptor substitution is effective in modifying the state energies. We are able to design molecules with 2Π ground states (NaOCC, H2NCC (2A″), HCSi, FCSi, etc.) and vary the 2Σ+–2Π energy gap over a 4 eV range. We find an inconsistency between bond order and bond dissociation energy measures of the bond strength in the Si-containing molecules; we provide an explanation through an analysis of the relevant potential energy curves., This computational study reveals that π-donor (acceptor) substituents (R) favor 2Π (2Σ+) ground state symmetry of acetylenyl radicals (RCC), facilitating RCC identification in interstellar space and combustion environments..

The recent σ-hole concept emphasizes the contribution of electrostatic attraction to noncovalent bonds, and implies that the electrostatic force has an angular dependency. Here a set of clusters, which includes hydrogen bonding, halogen bonding, chalcogen bonding, and pnicogen bonding systems, is investigated to probe the magnitude of covalency and its contribution to the directionality in noncovalent bonding. The study is based on the block-localized wavefunction (BLW) method that decomposes the binding energy into the steric and the charge transfer (CT) (hyperconjugation) contributions. One unique feature of the BLW method is its capability to derive optimal geometries with only steric effect taken into account, while excluding the CT interaction. The results reveal that the overall steric energy exhibits angular dependency notably in halogen bonding, chalcogen bonding, and pnicogen bonding systems. Turning on the CT interactions further shortens the intermolecular distances. This bond shortening enhances the Pauli repulsion, which in turn offsets the electrostatic attraction, such that in the final sum, the contribution of the steric effect to bonding is diminished, leaving the CT to dominate the binding energy. In several other systems particularly hydrogen bonding systems, the steric effect nevertheless still plays the major role whereas the CT interaction is minor. However, in all cases, the CT exhibits strong directionality, suggesting that the linearity or near linearity of noncovalent bonds is largely governed by the charge-transfer interaction whose magnitude determines the covalency in noncovalent bonds. © 2015 Wiley Periodicals, Inc.

We investigated the nature of the cohesive energy between graphane sheets via multiple CH···HC interactions, using density functional theory (DFT) including dispersion correction (Grimme's D3 approach) computations of [n]graphane σ dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical π/π interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (ΔE(F)) composed of electrostatic and Pauli repulsion interactions, polarization (ΔE(pol)), charge-transfer interaction (ΔE(CT)), and dispersion effects (ΔE(disp)). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the σ(CH) → σ*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 Å. The ΔE(CT) term, which accounts for ∼15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic "glue" for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the "double faced adhesive tape" style of charge transfer interactions was also observed among graphene sheets in which it accounts for ∼18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH···HC interactions, or as a function of the number of C-H bonds.

Typical hydrogen and halogen bonds exhibit red-shifts of their vibrational frequencies upon the formation of hydrogen and halogen bonding complexes (denoted as D···Y-A, Y = H and X). The finding of blue-shifts in certain complexes is of significant interest, which has led to numerous studies of the origins of the phenomenon. Because charge transfer mixing (i.e., hyperconjugation in bonding systems) has been regarded as one of the key forces, it would be illuminating to compare the structures and vibrational frequencies in bonding complexes with the charge transfer effect "turned on" and "turned off". Turning off the charge transfer mixing can be achieved by employing the block-localized wave function (BLW) method, which is an ab initio valence bond (VB) method. Further, with the BLW method, the overall stability gained in the formation of a complex can be analyzed in terms of a few physically meaningful terms. Thus, the BLW method provides a unified and physically lucid way to explore the nature of red- and blue-shifting phenomena in both hydrogen and halogen bonding complexes. In this study, a direct correlation between the total stability and the variation of the Y-A bond length is established based on our BLW computations, and the consistent roles of all energy components are clarified. The n(D) → σ*(Y-A) electron transfer stretches the Y-A bond, while the polarization due to the approach of interacting moieties reduces the HOMO-LUMO gap and results in a stronger orbital mixing within the YA monomer. As a consequence, both the charge transfer and polarization stabilize bonding systems with the Y-A bond stretched and red-shift the vibrational frequency of the Y-A bond. Notably, the energy of the frozen wave function is the only energy component which prefers the shrinking of the Y-A bond and thus is responsible for the associated blue-shifting. The total variations of the Y-A bond length and the corresponding stretching vibrational frequency are thus determined by the competition between the frozen-energy term and the sum of polarization and charge transfer energy terms. Because the frozen energy is composed of electrostatic and Pauli exchange interactions and frequency shifting is a long-range phenomenon, we conclude that long-range electrostatic interaction is the driving force behind the frozen energy term.

International audience; The nature of the single bond in the three isoelectronic coinage metal dimers Cu2, Ag2 and Au2 is investigated by means of the ab initio Breathing Orbital Valence Bond (BOVB) method, which allows one to calculate the respective contributions of the covalent and ionic structures to the total wave function, as well as the resonance energy arising from their mixing. It is shown that the BOVB method at its highest level provides bond dissociation energies in very good agreement with reference CCSD(T) values for the three dimers. It is also found that the covalent/ionic resonance energy is important in all three cases, contributing to 40-50% to the total bonding energy, thus qualifying the bonds in Cu2 and Au2 as quasi-charge-shift bonds, and that of Ag2 as a borderline case in-between classical covalent bond and charge-shift one. These results are further confirmed by analyses of the wave functions in terms of the Atoms-in-Molecule theory, which show that the Laplacian of the density at the bond critical point is large and positive in all three cases, which classifies the three bonds as charge-shift bonds within this theory.

The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds.

The charge-shift bonding (CSB) concept was originally discovered through valence bond (VB) calculations. Later, CSB was found to have signatures in atoms-in-molecules and electron-localization-function and in experimental electron density measurements. However, the CSB concept has never been derived from a molecular orbital (MO)-based theory. We now provide a proof of principle that an MO-based approach enables one to derive the CSB family alongside the distinctly different classical family of covalent bonds. In this bridging energy decomposition analysis, the covalent-ionic resonance energy, RECS, of a bond is extracted by cloning an MO-based purely covalent reference state, which is a constrained two-configuration wave function. The energy gap between this reference state and the variational TCSCF ground state yields numerical values for RECS, which correlate with the values obtained at the VBSCF level. This simple MO-based method, which only takes care of static electron correlation, is already sufficient for distinguishing the classical covalent or polar-covalent bonds from charge-shift bonds. The equivalence of the VB and MO-based methods is further demonstrated when both methods are augmented by dynamic correlation. Thus, it is shown from both MO and VB perspectives that the bonding in the CSB family does not arise from electron correlation. Considering that the existence of the CSB family is associated also with quite a few experimental observations that we already reviewed ( Shaik , S. , Danovich , D. , Wu , W. , and Hiberty , P. C. Nat. Chem. , 2009 , 1 , 443 - 449 ), the new bonding concept has passed by now two stringent tests. This derivation, on the one hand, supports the new concept and on the other, it creates bridges between the two main theories of electronic structure.

Does, or doesn't C2 break the glass ceiling of triple bonding? This work provides an overview on the bonding conundrum in C2 and on the recent discussions regarding our proposal that it possesses a quadruple bond. As such, we focus herein on the main point of contention, the 4th bond of C2, and discuss the main views. We present new data and an overview of the nature of the 4th bond--its proposed antiferromagnetically coupled nature, its strength, and a derivation of its bond energy from experimentally based thermochemical data. We address the bond-order conundrum of C2 arising from generalized VB (GVB) calculations by comparing it to HC≡CH, and showing that the two molecules behave very similarly, and C2 is in no way an exception. We analyse the root cause of the deviation of C2 from the Badger Rule, and demonstrate that the reason for the smaller force constant (FC) of C2 relative to HC≡CH has nothing to do with the bond energies, or with the number of bonds in the two molecules. The FC is determined primarily by the bond length, which is set by the balance between the bond length preferences of the σ- versus π-bonds in the two molecules. This interplay in the case of C2 clearly shows the fingerprints of the 4th bond. Our discussion resolves the points of contention and shows that the arguments used to dismiss the quadruple bond nature of C2 are not well founded.

This is a tutorial on the usage of valence bond (VB) diagrams for understanding chemical reactivity in general, and hydrogen atom transfer (HAT) reactivity in particular. The tutorial instructs the reader how to construct the VB diagrams and how to estimate HAT barriers from raw data, starting with the simplest reaction H + H2 and going all the way to HAT in the enzyme cytochrome P450. Other reactions are treated as well, and some unifying principles are outlined. The tutorial projects the unity of reactivity treatments, following Coulson's dictum "give me insight, not numbers", albeit with its modern twist: giving numbers and insight.

In response to the comment by Frenking and Hermann on our work in this journal (Chem. Eur J. 2016, 22, 4116) it is is shown once again that C

Poly(4-vinylpyridine) swollen in pyridine displays changes in electrical conductivity in response to white light and to low level thermal perturbation; protonation of the side-chain nitrogen is believed to play a role. Here we present spectroscopic evidence that the proton donor is the methyne group CH on the polymer chain.

To understand the dispersion stabilization of hydrocarbons in solids and of encumbered molecules, wherein CH···HC interactions act as sticky fingers, we developed here a valence bond (VB) model and applied it to analyze the H···H interactions in dimers of H2 and alkanes. The VB analysis revealed two distinct mechanisms of "dispersion." In the dimers of small molecules like H-H···H-H and H3CH···HCH3, the stabilization arises primarily due to the increased importance of the VB structures which possess charge alternation, e.g., C(+)H(-)···H(+)C(-) and C(-)H(+)···H(-)C(+), and hence bring about electrostatic stabilization that holds the dimer. This is consistent with the classical mechanism of oscillating dipoles as the source of dispersion interactions. However, in larger alkanes, this mechanism is insufficient to glue the two molecules together. Here, the "dispersion" interaction comes about through perturbational mixing of VB structures, which reorganize the bonding electrons of the two interacting CH bonds via recoupling of these electrons to H···H, C···C, and C···H "bonds." Finally, an attempt is made to create a bridge from VB to molecular orbital (MO) and local pair natural-orbital coupled electron pair approximation (LPNO-CEPA/1) analyses of the interactions, which bring about CH···HC binding.