11-cis retinal torsion: A QTAIM and stress tensor analysis of the S1 excited state

Maza, Julio R.; Jenkins, Samantha; Kirk, Steven R.

doi:10.1016/j.cplett.2016.04.051

Cited by 19 publications

(17 citation statements)

References 34 publications

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“…The ellipticity ε = | λ 1 |/| λ 2 | − 1, where λ 1 and λ 2 are the negative eigenvalues with corresponding eigenvectors e 1 and e 2 respectively that provide the relative accumulation of ρ ( r b ) in the two directions perpendicular to the bond‐path. Recently, for the 11‐cis retinal subjected to a torsion ±θ, we demonstrated that the e 2 eigenvector of the torsional BCP corresponded to the preferred + θ direction of rotation as defined by the PES profile …”

Section: Theory and Methodsmentioning

confidence: 94%

Next‐generation quantum theory of atoms in molecules for the ground and excited state of the ring‐opening of cyclohexadiene

Tian

Kirk

et al. 2018

Int J of Quantum Chemistry

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The factors underlying the experimentally observed branching ratio (70:30) of the (1,3‐cyclohexadiene) CHD → HT (1,3,5‐hexatriene) photochemical ring‐opening reaction are investigated. The ring‐opening reaction path is optimized by a high‐level multi‐reference DFT method and the density along the path is analyzed by the quantum theory of atoms in molecules (QTAIM) and stress tensor methods. The performed density analysis suggests that, in both S1 and S0 electronic states, there exists an attractive interaction between the ends of the fissile σ‐bond of CHD that steers the ring‐opening reaction predominantly in the direction of restoration of the ring. It is suggested that opening of the ring and formation of the reaction product (HT) can only be achieved when there is a sufficient persistent nuclear momentum in the direction of stretching of the fissile bond. As this orientation of the nuclear momentum vector can be expected relatively rare during the dynamics, this explains the observed low quantum yield of the ring‐opening reaction.

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Section: Theory and Methodsmentioning

confidence: 94%

Next‐generation quantum theory of atoms in molecules for the ground and excited state of the ring‐opening of cyclohexadiene

Tian

Kirk

et al. 2018

Int J of Quantum Chemistry

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“…The eigenvector e 3 indicates the direction of the bond path at the BCP; the most and least preferred directions of electron accumulation are e 2 and e 1 , respectively The ellipticity, ε provides the relative accumulation of ρ ( r b ) in the two directions perpendicular to the bond path at a BCP, defined as ε = |λ 1 |/|λ 2 | − 1 where λ 1 and λ 2 are negative eigenvalues of the corresponding eigenvectors e 1 and e 2 , respectively. Recently, the 11‐cis retinal was investigated and subjected to clockwise and counter‐clockwise torsions ±θ, where we demonstrated that the e 2 eigenvector of the torsional BCP corresponded to the preferred +θ direction of rotation defined by the PES profile . The total local energy density H ( r b )

H ((), {boldr}_{normalb}) = G ((), {boldr}_{normalb}) + V ((), {boldr}_{normalb}),

where G ( r b ) and V ( r b ) in Equation are the local kinetic and potential energy densities at a BCP, defines a degree of covalent character: A negative value for H ( r b ) < 0 for the closed‐shell interaction, a value of the Laplacian ∇ 2 ρ ( r b ) > 0, indicates a BCP with a degree of covalent character and conversely a positive value of H ( r b ) > 0 reveals a lack of covalent character for the closed‐shell BCP.…”

Section: Theory and Methodsmentioning

confidence: 99%

Next‐generation quantum theory of atoms in molecules for the photochemical ring‐opening reactions of oxirane

Xin

Azizi

et al. 2019

Int J of Quantum Chemistry

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The conical intersections corresponding to the C─O and C─C ring opening were optimized and the reaction paths traversing these intersections were obtained. Investigation of the C─O ring opening revealed that when traversing the lowest energy conical intersection, the reaction path returns to the closed ring geometry. The C─O path traversing the intersection featuring torsion of terminal CH2 group however, led to a ring‐opened geometry, an H‐shift and the formation of acetaldehyde that can undergo further dissociation. The observation of different reaction paths was explained by the 3‐D paths from quantum theory of atoms in molecules (QTAIM) that defined the most preferred direction of electronic motion that precisely tracked the mechanisms of bond breaking and formation throughout the photo‐reactions. The size, orientation, and location of these most preferred 3‐D paths indicated the extent and direction of motion of atoms, bonds, and the degree of torsion or planarity of a bond indicating a predictive ability.

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“…For the 11‐cis retinal subjected to a torsion ± α , we have recently demonstrated that the e 2 and e 1 σ eigenvectors of the torsional BCP corresponded to the preferred + α direction of rotation as defined by the PES profile . In this work, we choose to use the stress tensor response β σ because earlier it was found to produce more consistent results for torsion …”

Section: Theory and Methodsmentioning

confidence: 99%

“…In this regard, the methods of analyzing the total electronic density distributions ρ ( r ), such as the quantum theory of atoms in molecules QTAIM and stress tensor analysis methods, can provide complimentary information to the well established approaches analyzing the shape of the potential energy surfaces (PESs) of the ground and excited electronic states of the target compounds . Recently, some of us have developed QTAIM/stress tensor theory for use on the photoisomerization of the retinal chromophore and explored the implications of preferred direction of torsion − φ or + φ of the chromophore upon the photoexcitation …”

Section: Introductionmentioning

confidence: 99%

A QTAIM and stress tensor investigation of the torsion path of a light-driven fluorene molecular rotary motor

Momen

et al. 2016

J. Comput. Chem.

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The utility of the QTAIM/stress tensor analysis method for characterizing the photoisomerization of light driven molecular rotary machines is investigated on the example of the torsion path in fluorene molecular motor. The scalar and vector descriptors of QTAIM/stress tensor reveal additional information on the bonding interactions between the rotating units of the motor, which cannot be obtained from the analysis of the ground and excited state potential energy surfaces. The topological features of the fluorene motor molecular graph display that, upon the photoexcitation a certain increase in the torsional stiffness of the rotating bond can be attributed to the increasing topological stability of the rotor carbon atom attached to the rotation axle. The established variations in the torsional stiffness of the rotating bond may cause transfer of certain fraction of the torsional energy to other internal degrees of freedom, such as the pyramidalization distortion. © 2016 Wiley Periodicals, Inc.

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11-cis retinal torsion: A QTAIM and stress tensor analysis of the S1 excited state

Cited by 19 publications

References 34 publications

Next‐generation quantum theory of atoms in molecules for the ground and excited state of the ring‐opening of cyclohexadiene

Next‐generation quantum theory of atoms in molecules for the ground and excited state of the ring‐opening of cyclohexadiene

Next‐generation quantum theory of atoms in molecules for the photochemical ring‐opening reactions of oxirane

A QTAIM and stress tensor investigation of the torsion path of a light-driven fluorene molecular rotary motor

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