Dynamic treatment of vibrational energy relaxation in a heterogeneous and fluctuating environment

A computational approach to describe the energy relaxation of a high-frequency vibrational mode in a fluctuating heterogeneous environment is outlined. Extending previous work [H. Fujisaki, Y. Zhang, and J.E. Straub, J. Chem. Phys. {\bf 124}, 144910 (2006)], second-order time-dependent perturbation theory is employed which includes the fluctuations of the parameters in the Hamiltonian within the vibrational adiabatic approximation. This means that the time-dependent vibrational frequencies along an MD trajectory are obtained via a partial geometry optimization of the solute with fixed solvent and a subsequent normal mode calculation. Adopting the amide I mode of N-methylacetamide in heavy water as a test problem, it is shown that the inclusion of dynamic fluctuations may significantly change the vibrational energy relaxation. In particular, it is found that relaxation occurs in two phases, because for short times ($\lesssim$ 200 fs) the spectral density appears continuous due to the frequency-time uncertainty relation, while at longer times the discrete nature of the bath becomes apparent. Considering the excellent agreement between theory and experiment, it is speculated if this behavior can explain the experimentally obtained biphasic relaxation the amide I mode of N-methylacetamide.Comment: 24 pages, 7 figures, submitted to J. Chem. Phy

Quantum transport through single-molecule junctions with orbital degeneracies

We consider electronic transport through a single-molecule junction where the molecule has a degenerate spectrum. Unlike previous transport models, and theories a rate-equations description is no longer possible, and the quantum coherences between degenerate states have to be taken into account. We present the derivation and application of a master equation that describes the system in the weak-coupling limit and give an in-depth discussion of the parameter regimes and the new phenomena due to coherent on-site dynamics

Collisional Quantum Brownian Motion

We derive a quantum master equation from first principles to describe friction in one dimensional, collisional Brownian motion. We are the first to avoid an ill-defined square of the Dirac delta function by using localized wave packets rather than plane waves. Solving the Schr\"odinger equation for two colliding particles, we discover that the previously found position diffusion is not a physical process, but an artifact of the approximation of a coarse grained time scale, which in turn is needed to find Markkovian dynamics.Comment: 5 pages, 1 figur

Ancilla-assisted sequential approximation of nonlocal unitary operations

We consider the recently proposed "no-go" theorem of Lamata et al [Phys. Rev. Lett. 101, 180506 (2008)] on the impossibility of sequential implementation of global unitary operations with the aid of an itinerant ancillary system and view the claim within the language of Kraus representation. By virtue of an extremely useful tool for analyzing entanglement properties of quantum operations, namely, operator-Schmidt decomposition, we provide alternative proof to the "no-go" theorem and also study the role of initial correlations between the qubits and ancilla in sequential preparation of unitary entanglers. Despite the negative response from the "no-go" theorem, we demonstrate explicitly how the matrix-product operator(MPO) formalism provides a flexible structure to develop protocols for sequential implementation of such entanglers with an optimal fidelity. The proposed numerical technique, that we call variational matrix-product operator (VMPO), offers a computationally efficient tool for characterizing the "globalness" and entangling capabilities of nonlocal unitary operations.Comment: Slightly improved version as published in Phys. Rev.

The Accuracy of Perturbative Master Equations

We consider open quantum systems with dynamics described by master equations that have perturbative expansions in the system-environment interaction. We show that, contrary to intuition, full-time solutions of order-2n accuracy require an order-(2n+2) master equation. We give two examples of such inaccuracies in the solutions to an order-2n master equation: order-2n inaccuracies in the steady state of the system and order-2n positivity violations, and we show how these arise in a specific example for which exact solutions are available. This result has a wide-ranging impact on the validity of coupling (or friction) sensitive results derived from second-order convolutionless, Nakajima-Zwanzig, Redfield, and Born-Markov master equations.Comment: 6 pages, 0 figures; v2 updated references; v3 updated references, extension to full-time and nonlocal regime

Polaron Physics in Optical Lattices

We investigate the effects of a nearly uniform Bose-Einstein condensate (BEC) on the properties of immersed trapped impurity atoms. Using a weak-coupling expansion in the BEC-impurity interaction strength, we derive a model describing polarons, i.e., impurities dressed by a coherent state of Bogoliubov phonons, and apply it to ultracold bosonic atoms in an optical lattice. We show that, with increasing BEC temperature, the transport properties of the impurities change from coherent to diffusive. Furthermore, stable polaron clusters are formed via a phonon-mediated off-site attraction.Comment: 4 pages, 4 figure

Kochen-Specker Theorem for Finite Precision Spin One Measurements

Unsharp spin 1 observables arise from the fact that a residual uncertainty about the actual orientation of the measurement device remains. If the uncertainty is below a certain level, and if the distribution of measurement errors is covariant under rotations, a Kochen-Specker theorem for the unsharp spin observables follows: There are finite sets of directions such that not all the unsharp spin observables in these directions can consistently be assigned approximate truth-values in a non-contextual way.Comment: 4 page