A stress tensor eigenvector projection space for the (H2O)5 potential energy surface

Xu, Ting; Farrell, James D.; Momen, Roya; Azizi, Alireza; Kirk, Steven R.; Jenkins, Samantha; Wales, David J.

doi:10.1016/j.cplett.2016.11.028

Cited by 33 publications

(29 citation statements)

References 19 publications

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“…In this work we use the definition of the stress tensor proposed by Bader to investigate the stress tensor properties within the quantum theory of atoms in molecules (QTAIM) partitioning scheme . Earlier, it was found that the stress tensor properties such as the stiffness, S σ = | λ 1σ |/| λ 3σ | produced results that were in line with physical intuition as well as the stress tensor trajectories T σ ( s ) …”

Section: Introductionsupporting

confidence: 53%

“…The earlier attempt assumed that there was a one‐to‐one mapping between the QTAIM least preferred e 1 and most preferred e 2 directions of motions of the electronic charge density and the stress tensor e 1σ and e 2σ eigenvectors or even only the eigenvalues . Later investigations have demonstrated a lack of one to one mapping between the eigenvectors and eigenvalues of QTAIM and the stress tensor mapping . This confusion arose due to the accidental coincidence of the directions of the QTAIM e 2 and stress tensor e 2σ eigenvectors for bond‐paths with BCP s located away from the geometric midpoint that occurs for asymmetrical bonds.…”

Section: Introductionmentioning

confidence: 99%

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Stress tensor eigenvector following with next‐generation quantum theory of atoms in molecules

Huang

et al. 2018

Int J of Quantum Chemistry

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The eigenvectors of the electronic stress tensor have been identified as useful for the prediction of chemical reactivity because they determine the most preferred directions to move the bonds.A new 3-D vector based interpretation of the chemical bond that we refer to as the bond-path framework set B provides a version of the quantum theory of atoms in molecules (QTAIM) beyond the minimum definition for bonding that is particularly suitable for understanding changes in molecular electronic structure that occur during reactions. We demonstrate that the most preferred direction for bond motion using the stress tensor corresponds to the most compressible direction and not to the least compressible direction as previously reported. We show the necessity for a directional approach constructed using the eigenvectors along the entire bond-length and demonstrate the insufficiency of scalar measures for capturing the nature of the stress tensor within the QTAIM partitioning. K E Y W O R D Sbond-path framework set, QTAIM, stress tensor, torsion

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Section: Introductionsupporting

confidence: 53%

Section: Introductionmentioning

confidence: 99%

Stress tensor eigenvector following with next‐generation quantum theory of atoms in molecules

Huang

et al. 2018

Int J of Quantum Chemistry

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“…The background of QTAIM and next generation QTAIM (NG-QTAIM) [34], [50]- [55] with explanations is provided in theSupplementary Materials S1 , along with the procedure to generate the stress tensor trajectories T σ (s ). In this investigation we will use Bader's formulation of the stress tensor [32] within the QTAIM partitioning, which is a standard option in the QTAIM AIMAll [56] suite.…”

Section: Theoretical Background and Computational Detailsmentioning

confidence: 99%

Control of Chirality, Bond flexing and Anharmonicity in an Electric Field

Nie

et al. 2021

Preprint

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We located ‘hidden’ S-character chirality in formally achiral glycine using a vector-based interpretation of the total electronic charge density distribution. We induced the formation of stereoisomers in glycine by the application of an electric field. Control of chirality was indicated from the proportionate response to a non-structurally distorting electric field. The bond-flexing was determined to be a measure of bond strain, which could be a factor of three lower or higher, depending on the direction of the electric field, than in the absence of the electric field. The bond-anharmonicity was found to be approximately independent of the electric field. We also compared the formally achiral glycine with the chiral molecules alanine and lactic acid, quantifying the preferences for the S and R stereoisomers. The proportional response of the chiral discrimination to the magnitude and direction of the applied electric field indicated use of the chirality discrimination as a molecular similarity measure.

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“…Earlier, a stress tensor trajectories T σ in the stress tensor eigenvector projection space U σ [3, 4] methodology [5] was used to explain the relative differences in the intensities of the IR‐active modes of benzene [6–11] associated with changes in the dipole moment [7–9, 12, 13] where larger dipole moments were discovered to lead to greater IR‐active mode intensities. This T σ analysis was intended to complement the extensive studies of the vibrational modes of benzene that used semi‐empirical and ab initio methods [14–16] and theoretical treatments on the normal coordinate treatment of benzene [6, 17, 18], the conventional renderings of the four IR active modes of benzene and molecular graphs are provided in the Supporting Information S1.…”

Section: Introductionmentioning

confidence: 99%

Bond flexing, twisting, anharmonicity and responsivity for the infrared‐active modes of benzene

Yang

Kirk

et al. 2020

Int J of Quantum Chemistry

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In this investigation we have used next generation QTAIM to fully quantity the response to the four infrared (IR)‐active modes of all the bonding in benzene. This has been undertaken in terms of bond‐flexing, bond‐torsion and bond‐anharmonicity and the tendencies toward IR‐responsivity and IR‐non‐responsivity. Bond‐anharmonicity was not present for the CC bonds of the lowest frequency mode (721.57 cm−1) measured as the absence of relative sliding of the bond critical point (BCP) along the containing bond‐path. Additionally, bond‐flexing and bond‐anharmonicity were absent for this mode by the variation of the wrapping (torsion) of the {p,p′} path‐packet, referred to as the Precession K, along the bond‐path. The remaining three IR‐active mode possessed step‐like and variations in the K profiles and displayed anharmonic character. The presence of non‐nuclear attractors was detected for the IR‐active mode with frequency 1573.93 cm−1 with CC K profiles that most closely resemble those of the relaxed benzene.

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A stress tensor eigenvector projection space for the (H2O)5 potential energy surface

Cited by 33 publications

References 19 publications

Stress tensor eigenvector following with next‐generation quantum theory of atoms in molecules

Stress tensor eigenvector following with next‐generation quantum theory of atoms in molecules

Control of Chirality, Bond flexing and Anharmonicity in an Electric Field

Bond flexing, twisting, anharmonicity and responsivity for the infrared‐active modes of benzene

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