A model multilevel molecule described by two sets of rotational internal energy levels of different parity and degenerate ground states, coupled by a constant interaction, is considered, by assuming that the random collisions in a gas of identical molecules, provoke transitions between adjacent energy levels of the same parity. The prescriptions of the continuous time quantum random walk is applied to the single molecule, interpreted as an open quantum system, and the master equation driving its internal dynamics is built for a general distribution of random collision times. Over estimated long time scales, the dynamics of the coherence terms and the populations of the energy levels is evaluated analytically for relevant classes of non-Poissonian distributions of the collision times. Inverse power law relaxations and the inverse Zeno effect emerge over estimated long time scales and the stable asymptotic equilibrium configuration results to be independent of the distribution of the collision times.
We present an efficient theoretical method for calculating the time evolution of the density matrix of a multilevel quantum system weakly interacting with incoherent light. The method combines the Bloch-Redfield theory with a partial secular approximation for one-photon coherences, resulting in a master equation that explicitly exposes the reliance on transition rates and the angles between transition dipole moments in the energy basis. The partial secular Bloch-Redfield master equation allows an unambiguous distinction between the regimes of quantum coherent vs. incoherent energy transfer under incoherent light illumination. The fully incoherent regime is characterized by orthogonal transition dipole moments in the energy basis, leading to a dynamical evolution governed by a coherence-free Pauli-type master equation. The coherent regime requires non-orthogonal transition dipole moments in the energy basis and leads to the generation of noise-induced quantum coherences and population-to-coherence couplings. As a first application, we consider the dynamics of excited state coherences arising under incoherent light excitation from a single ground state and observe population-to-coherence transfer and the formation of non-equilibrium quasisteady states in the regime of small excited state splitting. Analytical expressions derived earlier for the V-type system [T. V. Tscherbul and P. Brumer, Phys. Rev. Lett. 113, 113601 (2014)] are found to provide a nearly quantitative description of multilevel excited-state populations and coherences in both the small- and large-molecule limits.
Multiphoton excitation and dissociation of large molecules under collisionless conditions is discussed in terms of an intercontinuum random coupling model. The mathematical approach described in a previous paper is used to obtain the general solution for a system of consecutively coupled discrete states, quasicontinuous manifolds, and continuous (dissociative) manifolds of molecular levels (eigenstates of the total molecular Hamiltonian), where the radiative coupling matrix elements are assumed to be given as a linear combination of smoothly varying and randomly varying (over level indices in the molecular manifolds) components. In the range of discrete molecular levels the time evolution is coherent and described in terms of the optical Bloch equation. In the quasicontinuous and continuous ranges the time evolution may be described in terms of Markoffian kinetic equations for the number of photons absorbed by the molecule, provided that the intramolecular vibrational relaxation widths associated with the optically active molecular modes is much larger than the Rabi frequency associated with the excitation of these modes. The kinetic evolution itself consists of direct multiphoton excitation processes (simultaneous transitions from the upper discrete levels to all higher energy molecular manifolds) resulting from the smooth component in the radiative coupling, and a consecutive excitation process described by the Pauli master equation with rates given by the golden rule expression. The interaction which enters into the golden rule expression is the variance in the radiative coupling. The direct excitation component contributes a negligible part of the overall excitation even if the random and smooth radiative coupling components are comparable. The resulting incoherent time evolution of the multiphoton excitation process is consistent with available experimental results. Coherent effects in the time evolution are expected for higher radiation field intensities, where the Rabi frequency becomes comparable to the intramolecular vibrational relaxation rate.
We present a formalism to analyze the effects of collisions and intramolecular energy transfer and dephasing processes (
T1 and
T2 relaxation) on level-population dynamics and unimolecular decay of laser-driven gas molecules. Utilizing a Boltzmann or optical Bloch equation for the density matrix to describe laser excitation of a relaxing multilevel absorber, we develop a generalized master equation (GME) to describe the dynamics of level population evolution for multilevel absorbers having arbitrary numbers of quantum levels
N. Because the resulting level-population equations explicitly retain phase memory, the effect of complete or partial phase-coherent driving or incoherent driving by the laser field are all included within the GME solutions. The formalism provides straightforward means to calculate time-dependent solutions for arbitrary
N, where a single expression is valid on transient, post transient, approach to steady state, and steady-state time scales. We illustrate the behavior of these solutions for the special case of three- and eight-level systems, but the method is not restricted with regard to number of levels. In both this and the following paper, we use specific examples and general arguments to show that an ordinary master equation (OME) is invalid even under apparently favorable conditions including saturating field strengths. We demonstrate that, for an
N-level absorber with given coupling elements, there are
2N [or
2(N+1)] independent saturation solutions and that special conditions on the relaxation times are required to produce the ordinary equal-population solution. Explicit forms for the steady-state radiative-transition matrix $W(\ensuremath{\lambda}=0)$ are derived for arbitrary
N, and general arguments are given to show that the correct description of the dynamics given by the GME results from matrix singularities in $W(\ensuremath{\lambda}=0)$ which can never occur in an OME or similar rate equations.
We derive and discuss the behavior of several multilevel models relevant to the problem of molecular multiphoton excitation under the action of a quasimonochromatic laser field, the amplitude of which rises slowly and falls rapidly on a certain internal time scale. Our method is suitable for the numerical solution of problems involving the adiabatic excitation of large multilevel systems. We find adiabatic inversion to be a general characteristic of the models considered. The fact that adiabatic inversion is accompanied by marked qualitative and quantitative changes in the expectation value of the dipole operator makes our results useful for understanding the propagation of laser pulses. An explicit expression that is especially convenient for numerical evaluation is presented for determining the limiting internal time scale, which is determined by the energy levels and transition moments of the system and the laser frequency. We illustrate the criterion for adiabatic inversion by applying it to a particular multilevel model. From a density-matrix treatment we conclude that collisional damping destroys the coherence required for adiabatic inversion. On the basis of our results we believe that the adiabatic approximation may be appropriate for some experiments of current interest.
In the framework of an exactly soluble model, one considers a typical problem of the interaction between radiation and matter: the dynamics of population in a multilevel quantum system subject to a time dependent perturbation. The algebraic structure of the model is taken richly enough, such that there exists a strong argument in favor of the fact that the behavior of the system in the asymptotic of long time has a universal character, which is system-independent and governed by the functional property of the time dependence exclusively. Functional properties of the excitation time dependence, resulting in the regimes of resonant excitation, random walks, and dynamic localization, are identified. Moreover, an intermediate regime between the random walks and the localization is identified for the polyharmonic excitation at frequencies given by the Liouville numbers.