A Unified Perspective on the Nature of Bonding in Pairwise Interatomic Interactions

Lucchese, Robert R.; Rosales, C. K.; Rivera‐Rivera, Luis A.; McElmurry, Blake A.; Bevan, J. W.; Walton, Jay R.

doi:10.1021/jp505985x

Cited by 16 publications

(34 citation statements)

References 67 publications

(137 reference statements)

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“…Initially, the concept of canonical potential was introduced to give a unified perspective on a range of ground state electronic potentials in diatomic molecules from CO, H to van der Waals, hydrogen bonded and halogen bonded pairwise interactions [13]. In subsequent studies this canonical approach was developed further generalized and improved [12,14] and its accuracy tested to high level within the Born-Oppenheimer approximation for molecules with few electrons.…”

Section: Discussionmentioning

confidence: 99%

“…These investigations explored the concept of a canonical potential strictly within the Born-Oppenheimer approximation for the most accurate available ground electronic state pairwise intermolecular potentials in H 2 , HeH + , and LiH [12]. Explicit canonically-based transformations have also been developed for transformation to a canonical potential for both these diatomics as well as two body intermolecular interactions [13,14]. The latter include several categories of bonding from van der Waals, hydrogen and halogen bonded 3 systems.…”

Section: Introductionmentioning

confidence: 99%

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A canonical approach to forces in molecules

et al. 2016

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In a previous study, we introduced a generalized formulation for canonical transformations and spectra to investigate the concept of canonical potentials strictly within the Born-Oppenheimer approximation. Data for the most accurate available ground electronic state pairwise intramolecular potentials in H 2 + , H 2 , HeH + , and LiH were used to rigorously establish such conclusions. Now, a canonical transformation is derived for the molecular force F(R) from the Hellmann-Feynman Theorem with H 2 + , the simplest molecule as molecular reference. These transformations are demonstrated to be inherently canonical to high accuracy but distinctly different from those corresponding to the respective potentials of H 2 , HeH + , and LiH. Further applications of this methodology to Mg 2 , benzene dimer and to water dimer are also considered within the radial limit. The implications of these results for electrostatic model of chemical bonding will be considered and discussed using this fundamentally force-based canonical approach.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A canonical approach to forces in molecules

et al. 2016

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“…Recently, we introduced the concept of a pairwise canonical potential [17] [17]. Explicit generalizations to all pairwise interactions studied, even at the asymptotic limit and extremely accurate strictly Born-Oppenheimer calculations have now been referenced to H 2 + [18,19].…”

Section: Introductionmentioning

confidence: 99%

Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann–Feynman Theorem

et al. 2016

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In recent work, force-based canonical approaches have given a unified but different viewpoint on the nature of bonding in pairwise interatomic interactions. The concept of a pairwise canonical potential in these cases was defined for a class of molecules referred to a dimensionless function obtained from each molecule by a readily invertible algebraic transformation. Differing molecular categories (covalent, ionic, van der Waals, hydrogen and halogen bonding) of representative interatomic interactions in which binding energies ranging from 1.01 to 1072.03 kJ/mol have been modeled canonically giving a rigorous semi-empirical verification to high accuracy. However, the fundamental physical basis that is expected to provide the inherent characteristics of these canonical transformations have not yet been elucidated. We now show that canonical force distributions can be formulated from the perspective of the HellmannFeynman Theorem and discuss how such canonical approaches can be used to further explain the nature of chemical bonding in pairwise interatomic interactions.

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“…19 Different classes of representative ground electronic state pairwise interatomic interactions were referenced to a chosen canonical potential illustrating application of such transformations. Specifically, accurately determined potentials of the diatomic molecules H 2 , H 2 + , HF, LiH, argon dimer, and one-dimensional dissociative coordinates in intermolecular Ar− HBr, OC−HF, and OC−Cl 2 were investigated throughout their ground state bound potentials.…”

Section: Introductionmentioning

confidence: 99%

Canonical Potentials and Spectra within the Born–Oppenheimer Approximation

et al. 2015

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A generalized formulation of canonical transformations and spectra are used to investigate the concept of a canonical potential strictly within the Born-Oppenheimer approximation. Data for the most accurate available ground electronic state pairwise intermolecular potentials in H2, HD, D2, HeH(+), and LiH are used to rigorously evaluate such transformations. The corresponding potentials are generated explicitly using parameters calculated with algebraic functions from that of the single canonical potential of the simplest molecule, H2(+). The efficacy of this approach is further tested by direct comparison of the predicted eigenvalues of all vibrational states in the selected molecular systems considered with the corresponding most accurately known Born-Oppenheimer eigenvalues currently available. Deviations are demonstrated to be less than 2 cm(-1) for all vibrational states in H2, HD, D2, HeH(+), and LiH, with an average standard deviation of 0.27 cm(-1) for the 87 states considered. The implications of these results for molecular quantum chemistry are discussed.

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A Unified Perspective on the Nature of Bonding in Pairwise Interatomic Interactions

Cited by 16 publications

References 67 publications

A canonical approach to forces in molecules

A canonical approach to forces in molecules

Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann–Feynman Theorem

Canonical Potentials and Spectra within the Born–Oppenheimer Approximation

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