Research paperQTAIM and stress tensor bond-path framework sets for the ground and excited states of fulvene
Graphical abstract
Top: QTAIM bond-path frame-work set B corresponding to the C.Iplanar configuration, where the (p0,q0)-paths (left panel) for S0 and (p1,q1)-paths (middle panel) for the S1 states are presented with (p0,p1)-paths (pale-blue) and (q0,q1)-paths (magenta) with a magnification factor of ×5. Variations of the ellipticity ε profiles (right panel) for the S0 and S1 states along the bond-path (r) associated with the torsional C2-C6 BCP.
Bottom: The corresponding stress tensor Bσ are presented also with a magnification factor of ×5 and the variations of the stress tensor ellipticity εσ profiles (right panel).
Section snippets
Acknowledgements
The National Natural Science Foundation of China is gratefully acknowledged, project approval number: 21673071. The One Hundred Talents Foundation of Hunan Province and the aid program for the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province are also gratefully acknowledged for the support of S.J. and S.R.K.
References (31)
- et al.
In search of an intrinsic chemical bond
Comput. Theor. Chem.
(2015) - et al.
11-cis retinal torsion: a QTAIM and stress tensor analysis of the S1 excited state
Chem. Phys. Lett.
(2016) - et al.
The bond bundle in open systems
Int. J. Quantum Chem.
(2010) - J.H. Li, W.J. Huang, T. Xu, S.R. Kirk, S. Jenkins, Stress Tensor Eigenvector Following with Next-Generation Quantum...
Quantum topology of molecular charge distributions. III. The mechanics of an atom in a molecule
J. Chem. Phys.
(1980)Atoms in Molecules: a Quantum Theory
(1994)Energieimpulssatz der Materiewellen
Ann. Phys.
(1927)Die allgemeinen prinzipien der wellenmechanik
Handb. Phys.
(1958)Coordinate invariance, the differential force law, and the divergence of the stress-energy tensor
J. Chem. Phys.
(1975)- W.J. Huang et al., Next-Generation Quantum Theory of Atoms in Molecules for the Ground and Excited States of Fulvene,...
An electron-preceding perspective on the deformation of materials
J. Chem. Phys.
Dependence of the normal modes on the electronic structure of various phases of ice as calculated by ab initio methods
Can. J. Phys.
Identifying and Analyzing Intermolecular Bonding Interactions in van der Waals Molecules
J. Phys. Chem.
A bond path: a universal indicator of bonded Interactions
J. Phys. Chem. A
Bond paths are not chemical bonds
J. Phys. Chem. A
Cited by (21)
Ultra-fast laser pulses as a probe of electron dynamics: A next generation QTAIM perspective
2024, Chemical Physics LettersMixed chiral and achiral character in substituted ethane: A next generation QTAIM perspective
2022, Chemical Physics LettersChiral and steric effects in ethane: A next generation QTAIM interpretation
2022, Chemical Physics LettersCitation Excerpt :In this investigation we will consider the non-energy-based NG-QTAIM alternative to steric effects and hyper-conjugation of ethane to gain insights into the staggered structure of ethane by locating any Uσ-space isomers and or stereoisomers. The background of QTAIM and next generation QTAIM (NG-QTAIM) [22–28] is provided in the Supplementary Materials S1, including the procedure to generate the stress tensor trajectories Tσ(s). Bader’s formulation of the stress tensor [29] and NG-QTAIM is a standard option in the AIMAll QTAIM package [30] and is used in this investigation because of the superior performance of the stress tensor compared with the Hessian of ρ(r) for distinguishing the S and R stereoisomers of lactic acid [31].
Theory developments and applications of next-generation QTAIM (NG-QTAIM)
2022, Advances in Quantum Chemical Topology Beyond QTAIMBond-path-rigidity and bond-path-flexibility of the ground state and first excited state of fulvene
2021, Chemical Physics LettersCitation Excerpt :This correlation between △Q1 and △B however, does not hold for the S1 state. This indicates an inherent asymmetry for the S1 state between the △B, BCP sliding, anharmonicity, and the △Q1 resulting in an unpredictable direction of the variation in the bond-path rigidity for the S1 state in agreement with our earlier work [2]. The greater decrease in the torsion C2-C6 BCP bond-path rigidity for the S1 compared with the S0 state, from the decrease in the precession values K, as a function of increasing torsion θ indicates that the photo-excitation facilitates the torsion.
The role of the natural transition orbital density in the S<inf>0</inf> → S<inf>1</inf> and S<inf>0</inf> → S<inf>2</inf> transitions of fulvene with next generation QTAIM
2020, Chemical Physics LettersCitation Excerpt :The current investigation on the differing reaction pathways in the first two excited states is undertaken using the next generation QTAIM, (NG-QTAIM) 3-D vector-based interpretation of the chemical bond, within the QTAIM[5] framework, referred to as the bond-path framework set B. The QTAIM bond-path framework sets B and the stress tensor Bσ were also found previously to provide a quantitative 3-D rendering of the bonding consistent with the chemical bonding insights provided by using Lewis structures of fulvene with double/single bond and resonance representations of S0 and S1 states for the values of torsion θ = 0.0° (FC) and 64.3° (CItorsion) along the excited state deactivation minimum energy path (MEP) [6]. The 64.3° CItorsion geometry represents the minimum energy conical intersection along a seam connecting all torsion angles [7] The new QTAIM B was used to demonstrate for fulvene that the ground state S0 and excited state S1 bonding existed on a continuous spectrum rather than as polar extremes, as presented on the Lewis structures.