Rotation-Induced Breakdown of Torsional Quantum Control

Control of the torsional angles of nonrigid molecules is key for the development of emerging areas like molecular electronics and nanotechnology. Based on a rigorous calculation of the rotation-torsion-Stark energy levels of nonrigid biphenyl-like molecules, we show that, unlike previously believed, instantaneous rotation-torsion-Stark eigenstates of such molecules, interacting with a strong laser field, present a large degree of delocalization in the torsional coordinate even for the lowest energy states. This is due to a strong coupling between overall rotation and torsion leading to a breakdown of the torsional alignment. Thus, adiabatic control of changes on the planarity of this kind of molecule is essentially impossible unless the temperature is on the order of a few Kelvin

Intrinsically biased electrocapacitive catalysis

We propose the application of the contact potential from metal-metal junctions or the built-in potential of semiconductor p-np-n junctions to induce or catalyze chemical reactions. Free of external sources, this intrinsic potential across microscale and nanoscale vacuum gaps establishes electric fields in excess of 10^7V/m. The electrostatic potential energy of these fields can be converted into useful chemical energy. As an example, we focus on the production of superthermal gas ions to drive reactions. Analysis indicates that this intrinsically biased electrocapacitive catalysis can achieve locally directed ion energies up to a few electron volts and local gas temperatureboosts in excess of 10^4K. Practical considerations for implementation and experimental tests are considered

Enhanced Molecular Orientation Induced by Molecular Anti-Alignment

We explore the role of laser induced anti-alignment in enhancing molecular orientation. A field-free enhanced orientation via anti-alignment scheme is presented, which combines a linearly polarized femtosecond laser pulse with a half-cycle pulse. The laser pulse induces transient anti-alignment in the plane orthogonal to the field polarization, while the half-cycle pulse leads to the orientation. We identify two qualitatively different enhancement mechanisms depending on the pulse order, and optimize their effects using classical and quantum models both at zero and non-zero temperature

Nuclear spin selective laser control of rotational and torsional dynamics

We explore the possibility of controlling rotational-torsional dynamics of non-rigid molecules with strong, non-resonant laser pulses and demonstrate that transient, laser-induced torsional alignment depends on the nuclear spin of the molecule. Consequently, nuclear spin isomers can be manipulated selectively by a sequence of time-delayed laser pulses. We show that two pulses with different polarization directions can induce either overall rotation or internal torsion, depending on the nuclear spin.Nuclear spin selective control of the angular momentum distribution may open new ways to separate and explore nuclear spin isomers of polyatomic molecules

Perfect coupling of light to surface plasmons with ultra-narrow linewidths

We examine the coupling of electromagnetic waves incident normal to a thin silver film that forms an oscillatory grating embedded between two otherwise uniform, semi-infinite half spaces. Two grating structures are considered, in one of which the mid point of the Ag film remains fixed whereas the thickness varies sinusoidally, while in the other the mid point oscillates sinusoidally whereas the film thicknesses remains fixed. On reducing the light wavelength from the long wavelength limit, we encounter signatures in the transmission, T, and reflection, R, coefficients associated with: i) the short-range surface plasmon mode, ii) the long-range surface plasmon mode, and iii) electromagnetic diffraction tangent to the grating. The first two features can be regarded as generalized (plasmon) Wood's anomalies whereas the third is the first-order conventional (electromagnetic) Wood's anomaly. The energy density at the film surface is enhanced for wavelengths corresponding to these three anomalies, particularly for the long range plasmon mode in thin films. When exciting the silver film with a pair of waves incident from opposite directions, we find that by adjusting the grating oscillation amplitude and fixing the relative phase of the incoming waves to be even or odd, T+R can be made to vanish for one or the other of the plasmon modes; this corresponds to perfect coupling (impedance matching in the language of electrical engineering) between the incoming light and these modes.Comment: 13 pages, 5 figures. accepted J. Chem. Phy

Vibrational effects in laser driven molecular wires

The influence of an electron-vibrational coupling on the laser control of electron transport through a molecular wire that is attached to several electronic leads is investigated. These molecular vibrational modes induce an effective electron-electron interaction. In the regime where the wire electrons couple weakly to both the external leads and the vibrational modes, we derive within a Hartree-Fock approximation a nonlinear set of quantum kinetic equations. The quantum kinetic theory is then used to evaluate the laser driven, time-averaged electron current through the wire-leads contacts. This novel formalism is applied to two archetypical situations in the presence of electron-vibrational effects, namely, (i) the generation of a ratchet or pump current in a symmetrical molecule by a harmonic mixing field and (ii) the laser switching of the current through the molecule.Comment: 12 pages, 7 figures, RevTeX4 require

Traversal time for electron tunneling in water

The traversal time for tunneling is a measure of the time during which the transmitted particle can be affected by interactions localized in the barrier. The Buttiker-Landauer approach, which estimates this time by imposing an internal clock on the system, has been applied so far for relatively simple 1-dimensional models. Here we apply this approach to estimate the traversal time for electron tunneling through a realistic 3-dimensional model of a water layer. Observed structure in the energy dependence of times computed reflects the existence of transient tunneling resonances associated with instantaneous water structures.Comment: 9 pages, 3 figures. Submitted to the Journal of Chemical Physic

Monotonically convergent optimal control theory of quantum systems under a nonlinear interaction with the control field

We consider the optimal control of quantum systems interacting non-linearly with an electromagnetic field. We propose new monotonically convergent algorithms to solve the optimal equations. The monotonic behavior of the algorithm is ensured by a non-standard choice of the cost which is not quadratic in the field. These algorithms can be constructed for pure and mixed-state quantum systems. The efficiency of the method is shown numerically on molecular orientation with a non-linearity of order 3 in the field. Discretizing the amplitude and the phase of the Fourier transform of the optimal field, we show that the optimal solution can be well-approximated by pulses that could be implemented experimentally.Comment: 24 pages, 11 figure

Squeezing of Atoms in a Pulsed Optical Lattice

We study the process of squeezing of an ensemble of cold atoms in a pulsed optical lattice. The problem is treated both classically and quantum-mechanically under various thermal conditions. We show that a dramatic compression of the atomic density near the minima of the optical potential can be achieved with a proper pulsing of the lattice. Several strategies leading to the enhanced atomic squeezing are suggested, compared and optimized.Comment: Latex, 9 pages, 10 figures, submitted to PR