3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Li<sub>m</sub>(<i>m</i>= 2–5), presented on the Ehrenfest force molecular graph

Azizi, Alireza; Momen, Roya; Kirk, Steven R.; Jenkins, Samantha

doi:10.1039/c9cp05066c

Cited by 17 publications

(26 citation statements)

References 44 publications

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“…Mode 14 is the only mode where the values of |∆ Q | are the same for the amplitudes ±1.0, although the precession K (and K ′) profiles are not symmetrical, see Figure 2. For mode 21, the presence of the non‐nuclear attractors ( NNA s) [22, 23] for both the C1C2 BCP bond‐path (amplitude = +1.0) and C4C5 BCP (amplitude = −1.0) bond‐path is noted and results in values of ±∆ Q comparable to the relaxed benzene and symmetrical precession K (and K ′) profiles, see Figure 3. Conversely, for mode 21 the bond‐paths lacking an NNA possess a greater range of the values of ±∆ Q and asymmetrical precession K (and K ′) profiles.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

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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“…The p and q are the 3‐D paths that are constructed from the values of the least ( e 1 ) and most ( e 2 ) preferred directions of electronic charge density accumulation along the bond‐path, referred to as r . For further discussions on the construction of bond‐path framework set B { p , q , r } [32–42], see Supporting Information S2.…”

Section: Theory and Methodsmentioning

confidence: 99%

Chirality–helicity of cumulenes: A non‐scalar charge density derived perspective

Xing

Azizi

Momen

et al. 2022

Int J of Quantum Chemistry

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We investigate the presence of helical character and chirality using a vector‐based charge density perspective instead of energetic or structural measures. The vector‐based perspective of the chemical bonding, constructed using the most preferred direction of charge density accumulation, finds the presence of induced symmetry‐breaking for α,ω‐disubstituted [4]cumulenes as the end groups are torsioned. The stress tensor trajectories Tσ(s) are used to provide the additional symmetry‐breaking required to quantify the degree and nature of the chirality and helical character. The S‐1,5‐dimethyl‐[4]cumulene contains a very low degree of chiral character but significant axiality(helicity) resulting in a weakly helical morphology of the corresponding Tσ(s). The (‐)S(‐), (+)S(‐) and (+)S(+) conformations of S‐1,5‐diamino‐[4]cumulene contain very significant degrees of both chirality and helical character resulting in helical morphology of the corresponding Tσ(s). We discuss the consequences for the Tσ(s) in locating chiral character in these molecules in future experiment investigations.

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“…The p and q are the 3-D paths that are constructed from the values of the least (e 1 ) and most (e 2 ) preferred directions of electronic charge density accumulation along the bond-path, referred to as r . For further discussions on the construction of bond-path framework set B{p ,q ,r } [31][32][33][34][35][36][37][38][39][40][41] , see the Supplementary Materials S2 .…”

Section: Theory and Methodsmentioning

confidence: 99%

Chirality-Helicity of Cumulenes: A Non-Scalar Charge Density Derived Perspective

Xing

Azizi

Momen

et al. 2021

Preprint

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We investigate the presence of helical character and chirality using a vector-based charge density perspective instead of energetic or structural measures. The vector-based perspective of the chemical bonding, constructed using the most preferred direction of charge density accumulation, finds the presence of induced symmetry-breaking for α,ω-disubstituted [4]cumulenes as the end groups are torsioned. The stress tensor trajectories Tσ(s) are used to provide the additional symmetry-breaking required to quantify the degree and nature of the chirality and helical character. We find an absence of chirality for [4]cumulene but a very significant degree of axiality as demonstrated by the purely axial form of the Tσ(s) indicating a lack of helical character. The S-1,5-dimethyl-[4]cumulene contains a very low degree of chiral character but significant axiality(helicity) resulting in a weakly helical morphology of the corresponding Tσ(s). The (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene contain very significant degrees of both chirality and helical character resulting in helical morphology of the corresponding Tσ(s). The chirality assignments are in agreement with the Cahn–Ingold–Prelog (CIP) classifications for the (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene. We discuss the consequences for the Tσ(s) in locating chiral character in these molecules in future experiment investigations.

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3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Li_m(m= 2–5), presented on the Ehrenfest force molecular graph

Cited by 17 publications

References 44 publications

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

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

Chirality–helicity of cumulenes: A non‐scalar charge density derived perspective

Chirality-Helicity of Cumulenes: A Non-Scalar Charge Density Derived Perspective

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3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Lim(m= 2–5), presented on the Ehrenfest force molecular graph

Cited by 17 publications

References 44 publications

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

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

Chirality–helicity of cumulenes: A non‐scalar charge density derived perspective

Chirality-Helicity of Cumulenes: A Non-Scalar Charge Density Derived Perspective

Contact Info

Product

Resources

About

3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Li_m(m= 2–5), presented on the Ehrenfest force molecular graph