Fewest switches adiabatic surface hopping as applied to vibrational energy relaxation

In this contribution quantum/classical surface hopping methodology is applied to vibrational energy relaxation of a quantum oscillator in a classical heat bath. The model of a linearly damped (harmonic) oscillator is chosen which can be mapped onto the Brownian motion (Caldeira-Leggett) Hamiltonian. In the simulations Tully's fewest switches surface hopping scheme is adopted with inclusion of dephasing in the adiabatic basis using a simple decoherence algorithm. The results are compared to the predictions of a Redfield-type quantum master equation modeling using the classical heat bath force correlation function as input. Thereby a link is established between both types of quantum/classical approaches. Viewed from the latter perspective, surface hopping with dephasing may be interpreted as "on-the-fly" stochastic realization of a quantum/classical Pauli master equation.     

Optimal control for maximally creating and maintaining a superposition state of a two-level system under the influence of Markovian decoherence

Reducing decoherence is an essential step toward realizing general-purpose quantum computers beyond the present noisy intermediate-scale quantum (NISQ) computers. To this end, dynamical decoupling (DD) approaches in which external fields are applied to qubits are often adopted. We numerically study DD using a two-level model system (qubit) under the influence of Markovian decoherence by using quantum optimal control theory with slightly modified settings, in which the physical objective is to maximally create and maintain a specified superposition state in a specified control period. An optimal pulse is numerically designed while systematically varying the values of dephasing, population decay, pulse fluence, and control period as well as using two kinds of objective functionals. The decrease in purity due to the decoherence limits the ability to maintain a coherent superposition state; we refer to the state of maximal purity that can be maintained as the saturated value. The optimally shaped pulse minimizes the negative effect of decoherence by gradually populating and continuously replenishing the state of saturated purity.     

Communication: Decoherence in a nonequilibrium environment: an analytically solvable model

We describe an analytically solvable model of quantum decoherence in a nonequilibrium environment. The model considers the effect of a bath driven from equilibrium by, for example, an ultrafast excitation of a quantum chromophore. The nonequilibrium response of the environment is represented by a nonstationary random function corresponding to the fluctuating transition frequency between two quantum states coupled to the surroundings. The nonstationary random function is characterized by a Fourier series with the phase of each term starting initially with a definite value across the ensemble but undergoing random diffusion with time. The decay of the off-diagonal density matrix element is shown to depend significantly on the particular pattern of initial phases of the terms in the Fourier series, or equivalently, the initial phases of bath modes coupled to the quantum subsystem. This suggests the possibility of control of quantum decoherence by the detailed properties of an environment that is driven from thermal equilibrium.     

Two-dimensional spectroscopy can distinguish between decoherence and dephasing of zero-quantum coherences

Recent experiments on a variety of photosynthetic antenna systems have revealed that coherences among electronic states persist longer than previously anticipated. In an ensemble measurement, the observed dephasing of a coherent state can occur because of either disorder across the ensemble or decoherence from interactions with the bath. Distinguishing how much such disorder affects the experimentally observed dephasing rate is paramount for understanding the role that quantum coherence may play in energy transfer through these complexes. Here, we show that two-dimensional electronic spectra can distinguish between the limiting cases of homogeneous dephasing (decoherence) and inhomogeneous dephasing by examining how the quantum beat frequency changes within a cross peak. For the antenna complex LH2 isolated from Rhodobacter sphaeroides , we find that dephasing of the coherence between the B850 and B800 rings arises predominantly from inhomogeneity. In contrast, within the Fenna-Matthews-Olson (FMO) complex from Chlorobium tepidum , dephasing of the coherence between the first two excitons appears quite homogeneous. Thus, the observed dephasing rate sets an upper bound on decoherence for the LH2 complex while establishing both an upper and lower bound for the FMO complex.     

Decoherence effects in reactive scattering

Decoherence effects on quantum and classical dynamics in reactive scattering are examined using a Caldeira-Leggett type model. Through a study of the dynamics of the collinear H + H2 reaction and the transmission over simple one-dimensional barrier potentials, we show that decoherence leads to improved agreement between quantum and classical reactions and transmission probabilities, primarily by increasing the energy dispersion in a well-defined way. Increased potential nonlinearity is seen to require larger decoherence in order to attain comparable quantum-classical agreement.     

Surface-hopping dynamics and decoherence with quantum equilibrium structure

In open quantum systems, decoherence occurs through interaction of a quantum subsystem with its environment. The computation of expectation values requires a knowledge of the quantum dynamics of operators and sampling from initial states of the density matrix describing the subsystem and bath. We consider situations where the quantum evolution can be approximated by quantum-classical Liouville dynamics and examine the circumstances under which the evolution can be reduced to surface-hopping dynamics, where the evolution consists of trajectory segments exclusively evolving on single adiabatic surfaces, with probabilistic hops between these surfaces. The justification for the reduction depends on the validity of a Markovian approximation on a bath averaged memory kernel that accounts for quantum coherence in the system. We show that such a reduction is often possible when initial sampling is from either the quantum or classical bath initial distributions. If the average is taken only over the quantum dispersion that broadens the classical distribution, then such a reduction is not always possible.     

Electronic decoherence time for non-Born-Oppenheimer trajectories

An expression is obtained for the electronic decoherence time of the reduced density electronic matrix in mixed quantum-classical molecular-dynamics simulations. The result is obtained by assuming that decoherence is dominated by the time dependence of the overlap of minimum-uncertainty packets and then maximizing the rate with respect to the parameters of the wave packets. The expression for the decay time involves quantities readily available in non-Born-Oppenheimer molecular-dynamics simulations, and it is shown to have a reasonable form when compared with two other formulas for the decay time that have been previously proposed.     

Time-resolved coherent anti-Stokes Raman-scattering measurements of I2 in solid Kr: vibrational dephasing on the ground electronic state at 2.6-32 K

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in the dephasing rate of v = 2 as the temperature is lowered to T = 2.6 K is taken as a clear indication of lattice-strain-induced inhomogeneity of the ensemble coherence.     

On the observation and origin of kinetic isotope effects in exchange dephasing: motional collapse of vibrational structure for SF6 isolated in a xe

High-resolution infrared spectra of SF₆ in a xenon matrix give evidence for dynamic exchange among trapping sites on the IR time scale. A ³²S-³⁴S kinetic isotope effect has been observed and attributed to differences in the dephasing mode frequencies and the resulting disparity in coupling to the phonon bath.     

Electronic coherence dynamics in trans-polyacetylene oligomers

Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.     

Theory of "laser distillation" of enantiomers: purification of a racemic mixture of randomly oriented dimethylallene in a collisional environment

Enantiomeric control of 1,3 dimethylallene in a collisional environment is examined. Specifically, our previous "laser distillation" scenario wherein three perpendicular linearly polarized light fields are applied to excite a set of vib-rotational eigenstates of a randomly oriented sample is considered. The addition of internal conversion, dissociation, decoherence, and collisional relaxation mimics experimental conditions and molecular decay processes. Of greatest relevance is internal conversion which, in the case of dimethylallene, is followed by molecular dissociation. For various rates of internal conversion, enantiomeric control is maintained in this scenario by a delicate balance between collisional relaxation of excited dimethylallene that enhances control and collisional dephasing, which diminishes control.     

Quantum stochastic theory of exchange dephasing model for a vibrating molecule in dense medium

The exchange dephasing model is investigated theoretically. An equation of motion satisfied by a reduced density matrix for the observed high-frequency mode is derived by a cumulant perturbation expansion method up to fourth order. The calculation shows a temperature dependence of the width and shift of the spectral line.