On the connection between probability density analysis, QTAIM, and VB theory

Reuter, Leonard; Lüchow, Arne

doi:10.1039/d0cp02209h

Cited by 18 publications

(19 citation statements)

References 87 publications

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“…is the total probability of its elements (i.e., its maxima). These probabilities compare well to the weights of valence bond theory [12]. For larger systems, it is often advantageous to restrict the elements a ∈ A in (5) and (6) to a subsetÃ ⊂ A (i.e., a ∈Ã).…”

Section: Clustering Of Maximamentioning

confidence: 58%

“…These structures often agree with Lewis structures, and their importance can be evaluated by integrating the probability density over the respective maxima's basins of attraction [11]. The resulting probabilities, which can be obtained for any wave function, have shown to be in good agreement with the weights of VB theory [12]. As such, these dot structures depict electronic structure information hidden in the many-particle wave function in condensed form.…”

Section: Introductionmentioning

confidence: 73%

“…With PDA, the local maxima R * of p(R) are investigated. They partition the configuration space R into their basins of attraction Ω R * [9][10][11][12]. As such, a maximum is a representative configuration for the entire distribution of electron configurations constituting its surrounding basin.…”

Section: Maxima Basins Of Attraction and Probabilitiesmentioning

confidence: 99%

“…In contrast, the ionic maxima are not labeled as equivalent, since their equal shape and value is only due to spatial symmetry. For a CAS (2,2) wave function in the minimal basis of 1s orbitals, the probabilities are 2 × 49% for the two covalent and 2 × 1.3% for the two ionic maxima [12].…”

Section: Maxima Basins Of Attraction and Probabilitiesmentioning

confidence: 99%

“…These early works were picked up by Scemama and coworkers, who performed a topological investigation with quantum Monte Carlo [8]. Recently, probability density analysis (PDA) has been introduced [9][10][11][12] as the all-electron equivalent of the quantum theory of atoms in molecules (QTAIM) [13,14] focusing on the one-electron density. The question arises about what can be gained from all-electron in comparison to the one-electron methods that can be broadly categorized into electron density methods (e.g., QTAIM, electron localization function (ELF) [15]) and orbital localization methods (e.g., natural bond orbital (NBO) analysis [16]).…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Dot Structures Beyond the Lewis Picture

2021

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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.

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Section: Clustering Of Maximamentioning

confidence: 58%

Section: Introductionmentioning

confidence: 73%

Section: Maxima Basins Of Attraction and Probabilitiesmentioning

confidence: 99%

Section: Maxima Basins Of Attraction and Probabilitiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab Initio Dot Structures Beyond the Lewis Picture

2021

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Chemical Bond Overlap Descriptors From Multiconfiguration Wavefunctions

Santos‐Jr,

Kraka,

Moura

2024

J Comput Chem

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The chemical bond is a fundamental concept in chemistry, and various models and descriptors have evolved since the advent of quantum mechanics. This study extends the overlap density and its topological descriptors (OP/TOP) to multiconfigurational wavefunctions. We discuss a comparative analysis of OP/TOP descriptors using CASSCF and DCD‐CAS(2) wavefunctions for a diverse range of molecular systems, including X–O bonds in X–OH (XH, Li, Na, H2B, H3C, H2N, HO, F) and Li–X′ (XF, Cl, and Br). Results show that OP/TOP aligns with bonding models like the quantum theory of atoms in molecules (QTAIM) and local vibrational modes theory, revealing insights such as overlap densities shifting towards the more electronegative atom in polar bonds. The Li–F dissociation profile using OP/TOP descriptors demonstrated sensitivity to ionic/neutral inversion during Li–F dissociation, highlighting their potential for elucidating complex bond phenomena and offering new avenues for understanding multiconfigurational chemical bond dynamics.

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