Surface-mounted altitudinal molecular rotors in alternating electric field: single-molecule parametric oscillator molecular dynamics.

Molecular dynamics simulations of the response to oscillating electric field elicited from an altitudinal dipolar molecular rotor mounted on the Au(111) surface and previously studied experimentally in static fields show unidirectional rotation in one of the three pairs of conformational enantiomers. The simulations are based on the universal force field and take into account electronic friction in the metal through its effect on the image charges. The rotor consists of two cobalt sandwich posts whose upper decks carry a biphenyl-like rotator with a dipole moment perpendicular to the rotation axle, mounted parallel to the surface. A phase diagram of rotor performance at 10 K as a function of field frequency and amplitude contains five unidirectional rotation regions: synchronous, half-synchronous (every other cycle skipped), quarter-synchronous (only indistinctly), asynchronous, and essentially no response. The nature of the subharmonic "single-molecule parametric oscillator" behavior is understood in mechanistic detail. Simulations at higher temperatures distinguish the thermal ("Brownian") and driven regimes of rotation, elucidated in terms of time-dependent potential energy surfaces for the rotation.

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

[2]  B. Chirikov.  A universal instability of many-dimensional oscillator systems , 1979 .

[3]  Dominik Horinek,et al.  Dipolar and nonpolar altitudinal molecular rotors mounted on an Au(111) surface. , 2004, Journal of the American Chemical Society.

[4]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[5]  R. Astumian,et al.  Chemical peristalsis. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[6]  D. Hamann,et al.  Variational Calculation of the Image Potential near a Metal Surface , 1972 .

[7]  O. Gunnarsson,et al.  Sticking probability on metal surfaces: Contribution from electron-hole-pair excitations , 1980 .

[8]  M. Tomassone,et al.  ELECTRONIC FRICTION FORCES ON MOLECULES MOVING NEAR METALS , 1997 .

[9]  M. Head‐Gordon,et al.  Molecular dynamics with electronic frictions , 1995 .

[10]  Josef Michl,et al.  Molecular dynamics of a grid-mounted molecular dipolar rotor in a rotating electric field , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[11]  W. Goddard,et al.  Charge equilibration for molecular dynamics simulations , 1991 .

[12]  Josef Michl,et al.  [n]Staffanes: a molecular-size "Tinkertoy" construction set for nanotechnology. Preparation of end-functionalized telomers and a polymer of [1.1.1]propellane , 1988 .

[13]  Yinggang Li,et al.  Nonadiabatic effects in hydrogen diffusion in metals , 1992 .

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

[15]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[16]  S. Edwards,et al.  The Theory of Polymer Dynamics , 1986 .

[17]  Michael L. Klein,et al.  Simulation of a monolayer of alkyl thiol chains , 1989 .

[18]  H. Suhl,et al.  Brownian motion model of the interactions between chemical species and metallic electrons: Bootstrap derivation and parameter evaluation , 1975 .

[19]  Dominik Horinek,et al.  Molecular dynamics simulation of an electric field driven dipolar molecular rotor attached to a quartz glass surface. , 2003, Journal of the American Chemical Society.

[20]  M. Magnasco,et al.  Forced thermal ratchets. , 1993, Physical review letters.

[21]  A. Meijere,et al.  Strain and Its Implications in Organic Chemistry , 1989 .

[22]  W. Goddard,et al.  UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations , 1992 .

[23]  A. Credi,et al.  Molecular Devices and Machines , 2007, New Frontiers in Nanochemistry.

[24]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials , 1995 .

[25]  J. Hermans,et al.  REACTION FIELD MOLECULAR DYNAMICS SIMULATION WITH FRIEDMAN'S IMAGE CHARGE METHOD , 1995 .

[26]  H. Kramers.  Brownian motion in a field of force and the diffusion model of chemical reactions , 1940 .

[27]  Jorge V. José,et al.  Classical Dynamics: A Contemporary Approach , 1998 .

[28]  Josef Michl,et al.  Toward a molecular-size tinkertoy construction set. Preparation of terminally functionalized [n]staffanes from [1.1.1]propellane , 1992 .

[29]  David M. Ferguson,et al.  Constant temperature simulations using the Langevin equation with velocity Verlet integration , 1998 .

[30]  R. Astumian.  Adiabatic Theory for Fluctuation-Induced Transport on a Periodic Potential , 1996 .

[31]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .

[32]  Dominik Horinek,et al.  Artificial molecular rotors. , 2005, Chemical reviews.

[33]  Josef Michl,et al.  A MOLECULAR TINKERTOY CONSTRUCTION KIT : COMPUTER SIMULATION OF MOLECULAR PROPELLERS , 1997 .

[34]  P. Schleyer.  Encyclopedia of computational chemistry , 1998 .