QTAIM and Stress Tensor Characterization of Intramolecular Interactions Along Dynamics Trajectories of a Light-Driven Rotary Molecular Motor.

A quantum theory of atoms in molecules (QTAIM) and stress tensor analysis was applied to analyze intramolecular interactions influencing the photoisomerization dynamics of a light-driven rotary molecular motor. For selected nonadiabatic molecular dynamics trajectories characterized by markedly different S1 state lifetimes, the electron densities were obtained using the ensemble density functional theory method. The analysis revealed that torsional motion of the molecular motor blades from the Franck-Condon point to the S1 energy minimum and the S1/S0 conical intersection is controlled by two factors: greater numbers of intramolecular bonds before the hop-time and unusually strongly coupled bonds between the atoms of the rotor and the stator blades. This results in the effective stalling of the progress along the torsional path for an extended period of time. This finding suggests a possibility of chemical tuning of the speed of photoisomerization of molecular motors and related molecular switches by reshaping their molecular backbones to decrease or increase the degree of coupling and numbers of intramolecular bond critical points as revealed by the QTAIM/stress tensor analysis of the electron density. Additionally, the stress tensor scalar and vector analysis was found to provide new methods to follow the trajectories, and from this, new insight was gained into the behavior of the S1 state in the vicinity of the conical intersection.

[1]  A. Becke.  A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[2]  Samantha Jenkins,et al.  11- cis retinal torsion: A QTAIM and stress tensor analysis of the S 1 excited state , 2016 .

[3]  Michael Filatov,et al.  Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules , 2013, Journal of chemical theory and computation.

[4]  Mingxing Hu,et al.  A QTAIM and stress tensor investigation of the torsion path of a light‐driven fluorene molecular rotary motor , 2016, J. Comput. Chem..

[5]  Chérif F. Matta,et al.  Hydrogen–hydrogen bonding in biphenyl revisited , 2007 .

[6]  Samantha Jenkins,et al.  The response of the electronic structure to electronic excitation and double bond torsion in fulvene: a combined QTAIM, stress tensor and MO perspective. , 2014, Physical chemistry chemical physics : PCCP.

[7]  Auke Meetsma,et al.  Acceleration of a nanomotor: electronic control of the rotary speed of a light-driven molecular rotor. , 2005, Journal of the American Chemical Society.

[8]  Auke Meetsma,et al.  A redesign of light-driven rotary molecular motors. , 2008, Organic & biomolecular chemistry.

[9]  Samantha Jenkins,et al.  Spanning QTAIM topology phase diagrams of water isomers W4, W5 and W6. , 2011, Physical chemistry chemical physics : PCCP.

[10]  Samantha Jenkins,et al.  Quantum topology phase diagrams for molecules, clusters, and solids , 2013 .

[11]  Michael Filatov,et al.  Spin‐restricted ensemble‐referenced Kohn–Sham method: basic principles and application to strongly correlated ground and excited states of molecules , 2015 .

[12]  Walter Thiel,et al.  Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules. , 2014, The Journal of chemical physics.

[13]  Shubin Liu,et al.  Spanning set of silica cluster isomer topologies from QTAIM. , 2011, The journal of physical chemistry. A.

[14]  M. Barbatti.  Nonadiabatic dynamics with trajectory surface hopping method , 2011 .

[15]  R. Bader,et al.  Identifying and Analyzing Intermolecular Bonding Interactions in van der Waals Molecules , 1996 .

[16]  E. D. Isaacs,et al.  Covalency of the Hydrogen Bond in Ice: A Direct X-Ray Measurement , 1999 .

[17]  Tianlv Xu,et al.  Biphenyl: A stress tensor and vector‐based perspective explored within the quantum theory of atoms in molecules , 2015 .

[18]  Vincenzo Balzani,et al.  Light powered molecular machines. , 2009, Chemical Society reviews.

[19]  Samantha Jenkins,et al.  The chemical character of the intermolecular bonds of seven phases of ice as revealed by ab initio calculation of electron densities , 2000 .

[20]  Chérif F Matta,et al.  Hydrogen-hydrogen bonding: a stabilizing interaction in molecules and crystals. , 2003, Chemistry.

[21]  Jamie Conyard,et al.  Ultrafast dynamics in the power stroke of a molecular rotary motor. , 2012, Nature chemistry.

[22]  M. Filatov.  Ensemble DFT Approach to Excited States of Strongly Correlated Molecular Systems. , 2016, Topics in current chemistry.

[23]  Lingling Wang,et al.  Distinguishing and quantifying the torquoselectivity in competitive ring‐opening reactions using the stress tensor and QTAIM , 2016, J. Comput. Chem..

[24]  Paul W Ayers,et al.  An electron-preceding perspective on the deformation of materials. , 2009, The Journal of chemical physics.

[25]  Ilyas Absar,et al.  XVI. Representations of the Electron Density and its Topographical Features , 1977 .

[26]  Walter Thiel,et al.  Surface Hopping Excited-State Dynamics Study of the Photoisomerization of a Light-Driven Fluorene Molecular Rotary Motor. , 2011, Journal of chemical theory and computation.

[27]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[28]  G. G. Hall,et al.  Orthogonal trajectories of the electron density , 1977 .

[29]  J. F. Stoddart,et al.  Great expectations: can artificial molecular machines deliver on their promise? , 2012, Chemical Society reviews.

[30]  G. London,et al.  Rotary molecular motors: a large increase in speed through a small change in design. , 2010, The Journal of organic chemistry.

[31]  Walter Thiel,et al.  Semiempirical quantum–chemical methods , 2014 .

[32]  Massimo Olivucci,et al.  Directionality of Double-Bond Photoisomerization Dynamics Induced by a Single Stereogenic Center. , 2015, The journal of physical chemistry letters.

[33]  N. Harada,et al.  Light-driven monodirectional molecular rotor , 2022 .

[34]  S Gozem,et al.  Learning from photobiology how to design molecular devices using a computer. , 2014, Chemical Society reviews.

[35]  Chérif F. Matta,et al.  Fluorine-Fluorine Spin-Spin Coupling Constants in Aromatic Compounds: Correlations with the Delocalization Index and with the Internuclear Separation , 2005, J. Chem. Inf. Model..

[36]  Walter Thiel,et al.  Computational Design of a Family of Light-Driven Rotary Molecular Motors with Improved Quantum Efficiency , 2015, The journal of physical chemistry letters.

[37]  Gernot Frenking,et al.  The barrier to the methyl rotation in Cis‐2‐butene and its isomerization energy to Trans‐2‐butene, revisited , 2016, J. Comput. Chem..

[38]  D. Wales,et al.  A stress tensor eigenvector projection space for the (H 2 O) 5 potential energy surface , 2017 .

[39]  Walter Thiel,et al.  Implementation of a general multireference configuration interaction procedure with analytic gradients in a semiempirical context using the graphical unitary group approach , 2003, J. Comput. Chem..

[40]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[41]  Ben L Feringa,et al.  The art of building small: from molecular switches to molecular motors. , 2007, The Journal of organic chemistry.

[42]  H. Wegner,et al.  Attraction or Repulsion? London Dispersion Forces Control Azobenzene Switches. , 2015, Angewandte Chemie.

[43]  J. Tully.  Molecular dynamics with electronic transitions , 1990 .

[44]  Samantha Jenkins,et al.  Dependence of the normal modes on the electronic structure of various phases of ice as calculated by ab initio methods , 2003 .

[45]  Todd J. Martínez,et al.  Conical intersections and double excitations in time-dependent density functional theory , 2006 .

[46]  Walter Thiel,et al.  Description of Conical Intersections with Density Functional Methods. , 2016, Topics in current chemistry.

[47]  Auke Meetsma,et al.  Second generation light-driven molecular motors. Unidirectional rotation controlled by a single stereogenic center with near-perfect photoequilibria and acceleration of the speed of rotation by structural modification. , 2002, Journal of the American Chemical Society.

[48]  Massimo Olivucci,et al.  Designing conical intersections for light-driven single molecule rotary motors: from precessional to axial motion. , 2014, The Journal of organic chemistry.

[49]  R. Bader,et al.  Quantum topology of molecular charge distributions. III. The mechanics of an atom in a molecule , 1980 .

[50]  J. Pople,et al.  Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions , 1980 .

[51]  Walter Thiel,et al.  Orthogonalization corrections for semiempirical methods , 2000 .

[52]  Michael Filatov,et al.  Understanding the dynamics behind the photoisomerization of a light-driven fluorene molecular rotary motor. , 2010, The journal of physical chemistry. A.

[53]  Wesley R Browne,et al.  Making molecular machines work , 2006, Nature nanotechnology.