Dieter Cremer's contribution to the field of theoretical chemistry

Kraka, Elfi; Cremer, Dieter

doi:10.1002/qua.25849

Cited by 27 publications

(20 citation statements)

References 322 publications

(342 reference statements)

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“…Recent developments by Konkoli and Cremer ( Konkoli and Cremer, 1998a ; Konkoli and Cremer, 1998b ; Kraka et al, 2020 ) have allowed for the mass decoupling of the normal modes of vibration, to recast the eigenvectors onto a new set of modes, termed the local modes of vibration, that correlate directly with individual bond stretches, angle bends etc. Their work has shown that the resulting local-mode force constants thus obtained are a direct measure of bond strength ( Kraka and Cremer, 2019 ). Thus performing local mode analysis across a broad range of molecules (both energetic and non-energetic) provides information on the relationship between bond length and bond strength of the most common chemical bonds in EMs, which has the potential to be utilised for molecular design.…”

Section: Introductionmentioning

confidence: 99%

Towards Computational Screening for New Energetic Molecules: Calculation of Heat of Formation and Determination of Bond Strengths by Local Mode Analysis

et al. 2021

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The reliable determination of gas-phase and solid-state heats of formation are important considerations in energetic materials research. Herein, the ability of PM7 to calculate the gas-phase heats of formation for CNHO-only and inorganic compounds has been critically evaluated, and for the former, comparisons drawn with isodesmic equations and atom equivalence methods. Routes to obtain solid-state heats of formation for a range of single-component molecular solids, salts, and co-crystals were also evaluated. Finally, local vibrational mode analysis has been used to calculate bond length/force constant curves for seven different chemical bonds occurring in CHNO-containing molecules, which allow for rapid identification of the weakest bond, opening up great potential to rationalise decomposition pathways. Both metrics are important tools in rationalising the design of new energetic materials through computational screening processes.

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Section: Introductionmentioning

confidence: 99%

Towards Computational Screening for New Energetic Molecules: Calculation of Heat of Formation and Determination of Bond Strengths by Local Mode Analysis

et al. 2021

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“…3c-4e HVI bonding (3c-4e HVIB) draws comparisons to the secondary bonding interaction due to the weak bond strength, high reactivity, and long internuclear distances exceeding covalent bond lengths [37]. 3c-4e HVIB also shares similarities with non-covalent interactions, along with hydrogen bonding [38][39][40], XB [35,[41][42][43], pnicogen bonding [43][44][45], chalcogen bonding [43,46], and tetrel bonding [47]. XB is a non-covalent interaction between an electrophilic halogen (X) and a nucleophile with a lone pair (lp(A)) of donating electrons [42,43].…”

Section: Introductionmentioning

confidence: 99%

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

et al. 2019

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The intrinsic bonding nature of λ 3 -iodanes was investigated to determine where its hypervalent bonds fit along the spectrum between halogen bonding and covalent bonding. Density functional theory with an augmented Dunning valence triple zeta basis set ( ω B97X-D/aug-cc-pVTZ) coupled with vibrational spectroscopy was utilized to study a diverse set of 34 hypervalent iodine compounds. This level of theory was rationalized by comparing computational and experimental data for a small set of closely-related and well-studied iodine molecules and by a comparison with CCSD(T)/aug-cc-pVTZ results for a subset of the investigated iodine compounds. Axial bonds in λ 3 -iodanes fit between the three-center four-electron bond, as observed for the trihalide species IF 2 − and the covalent FI molecule. The equatorial bonds in λ 3 -iodanes are of a covalent nature. We explored how the equatorial ligand and axial substituents affect the chemical properties of λ 3 -iodanes by analyzing natural bond orbital charges, local vibrational modes, the covalent/electrostatic character, and the three-center four-electron bonding character. In summary, our results show for the first time that there is a smooth transition between halogen bonding → 3c–4e bonding in trihalides → 3c–4e bonding in hypervalent iodine compounds → covalent bonding, opening a manifold of new avenues for the design of hypervalent iodine compounds with specific properties.

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“…The well depth, which is the difference in energy between the local minimum and TS, can be regarded as the energy indicator for the kinetic stability of interanion interaction and a measurement of its strength as well. Alternatively, the local bond stretching force constant ( k ), − which basically stands for the curvature of an energy profile along the direction of a specified chemical bond, can be considered as an “in situ” indicator for the intrinsic bond strength. As k has provided novel insights into conventional and unusual chemical bonds, − it could serve as an indicator for interanion interactions in this work.…”

Section: Introductionmentioning

confidence: 99%

“…Profiles of electrostatic interactions and total interaction energies were further analyzed using the AMOEBA polarizable force field − with QM-based atomic multipoles, ,, aiming at a concise interpretation for these interanion phenomena. Based on our findings, a few novel complexes with attractive interanion contacts were constructed (9, 11, 13, and 15 in Scheme ) with a group of simplified molecular capsules. − In addition, the local bond stretching force constant ( k ) − as a new indicator for interanion H/XB was also inspected.…”

Section: Introductionmentioning

confidence: 99%

Classical Electrostatics Remains the Driving Force for Interanion Hydrogen and Halogen Bonding

et al. 2021

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Interanion hydrogen bonding (IAHB) and halogen bonding (IAXB) have emerged as a counterintuitive linker in a range of fascinating applications. Despite the overall repulsive (positive) binding energy, anions are trapped in a local minimum with its corresponding transition state (TS) preventing dissociation. In other words, the adduct of anions is metastable. Seemingly, the electrostatic paradigm and force field description of hydrogen/halogen bonding (HB/XB) are challenged, because of the preconceived Coulombic repulsion. Aiming at an insightful understanding of these interanion phenomena, we employed the energy decomposition approach based on the block-localized wavefunction method (BLW-ED) to investigate a series of exemplary interanion complexes. As expected, the key distinction from the conventional HB/XB lies in the electrostatic interaction, which is not increasingly repulsive as anions gradually approach to each other. Rather, there is a Coulombic barrier at a certain point. After this point, the electrostatic repulsion diminishes with the decreasing distance between anions. Differently, other energy components vary monotonically just like in conventional cases. The nonmonotonic characteristic of the electrostatic interaction in interanion complexes was reproduced using the multipole expansion in AMOEBA polarizable force field in which the state-specified atomic multipoles were adopted. This suggests that the nonmonotonicity can be well interpreted by classical electrostatic theory and there is no conceptual difference between conventional HB/XB and IAHB/IAXB. The stability of IAHB/ IAXB depends on the competition between the local attractive HB/XB and the global Coulombic repulsion of net charges, though there is cooperativity between these two contrasting forces. This concise model was supported by the attractive IAHB/IAXB in modified molecular capsules, which exhibit strong quadruple HB/XBs and a considerable distance between charged substituents.

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Dieter Cremer's contribution to the field of theoretical chemistry

Cited by 27 publications

References 322 publications

Towards Computational Screening for New Energetic Molecules: Calculation of Heat of Formation and Determination of Bond Strengths by Local Mode Analysis

Towards Computational Screening for New Energetic Molecules: Calculation of Heat of Formation and Determination of Bond Strengths by Local Mode Analysis

A Continuum from Halogen Bonds to Covalent Bonds: Where Do λ3 Iodanes Fit?

Classical Electrostatics Remains the Driving Force for Interanion Hydrogen and Halogen Bonding

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