Molecular dynamics of a grid-mounted molecular dipolar rotor in a rotating electric field

Classical molecular dynamics is applied to the rotation of a dipolar molecular rotor mounted on a square grid and driven by rotating electric field E(nu) at T approximately 150 K. The rotor is a complex of Re with two substituted o-phenanthrolines, one positively and one negatively charged, attached to an axial position of Rh(2)(4+) in a [2]staffanedicarboxylate grid through 2-(3-cyanobicyclo[1.1.1]pent-1-yl)malonic dialdehyde. Four regimes are characterized by a, the average lag per turn: (i) synchronous (a < 1/e) at E(nu) = /E(nu)/ > E(c)(nu) [E(c)(nu) is the critical field strength], (ii) asynchronous (1/e < a < 1) at E(c)(nu) > E(nu) > E(bo)(nu) > kT/mu;, [E(bo)(nu) is the break-off field strength], (iii) random driven (a approximately 1) at E(bo)(nu) > E(nu) > kT/mu, and (iv) random thermal (a approximately 1) at kT/mu > E(nu). A fifth regime, (v) strongly hindered, W > kT, E(mu), (W is the rotational barrier), has not been examined. We find E(bo)(nu)/kVcm(-1) approximately (kT/(mu))/kVcm(-1) + 0.13(nu/GHz)(1.9) and E(c)(nu)/kVcm(-1) approximately (2.3kT/(mu))/kVcm(-1) + 0.87(nu/GHz)(1.6). For nu > 40 GHz, the rotor behaves as a macroscopic body with a friction constant proportional to frequency, eta/eVps approximately 1.14 nu/THz, and for nu < 20 GHz, it exhibits a uniquely molecular behavior.