Search

The quantum dynamics of electron transfer in mixed-valence organic compounds is investigated using a reaction path model calibrated by constrained density functional theory (cDFT). Constrained DFT is used to define diabatic states relevant for describing the electron transfer, to obtain equilibrium structures for each of these states and to estimate the electronic coupling between them. The harmonic analysis at the diabatic minima yields normal modes forming the dissipative bath coupled to the electronic states. In order to decrease the system-bath coupling, an effective one dimensional vibronic Hamiltonian is constructed by partitioning the modes into a linear reaction path which connects both equilibrium positions and a set of secondary vibrational modes, coupled to this reaction coordinate. Using this vibronic model Hamiltonian, dissipative quantum dynamics is carried out using Redfield theory, based on a spectral density which is determined from the cDFT results. In a first benchmark case, the model is applied to a series of mixed-valence organic compounds formed by two 1,4-dimethoxy-3-methylphenylene fragments linked by an increasing number of phenylene bridges. This allows us to examine the coherent electron transfer in extreme situations leading to a ground adiabatic state with or without a barrier and therefore to the trapping of the charge or to an easy delocalization.

We compare the strategy found by the optimal control theory in a complex molecular system according to the active subspace coupled to the field. The model is the isomerization during a Cope rearrangement of Thiele's ester that is the most stable dimer obtained by the dimerization of methyl-cyclopentadienenylcarboxylate. The crudest partitioning consists in retaining in the active space only the reaction coordinate, coupled to a dissipative bath of harmonic oscillators which are not coupled to the field. The control then fights against dissipation by accelerating the passage across the transition region which is very wide and flat in a Cope reaction. This mechanism has been observed in our previous simulations [Chenel et al., J. Phys. Chem. A 116, 11273 (2012)]. We compare here, the response of the control field when the reaction path is coupled to a second active mode. Constraints on the integrated intensity and on the maximum amplitude of the fields are imposed limiting the control landscape. Then, optimum field from one-dimensional simulation cannot provide a very high yield. Better guess fields based on the two-dimensional model allow the control to exploit different mechanisms providing a high control yield. By coupling the reaction surface to a bath, we confirm the link between the robustness of the field against dissipation and the time spent in the delocalized states above the transition barrier.

In this work, we present optimal control calculations in a dissipative environment. To this end, the auxiliary density matrix method describing the dissipative quantum dynamics is combined with optimal control theory. The resulting approach, which is nonperturbative in the laser-system interaction, is applied to model the control of Cope's isomerization of the methyl-cyclopentadienylcarboxylate dimer, described as the motion along a one-dimensional reaction path. The construction of the reaction path model as well as the dipole moments required for the laser interaction are obtained from DFT quantum chemistry calculations. As a main result, we show that the proposed methodology, which includes the environment at the design stage of the control, leads to control fields which can react on dissipative effects during the dynamics and lead to an increased control objective, as compared to control fields obtained without dissipation. The chosen example is analyzed in detail, and the physical mechanisms of the control under dissipation are elucidated.

Within the context of vibrational molecular quantum computing, we investigate the implementation of a full addition of two binary digits and a carry that provides the sum and the carry out. Four qubits are necessary and they are encoded into four different normal vibrational modes of a molecule. We choose the bromoacetyl chloride molecule because it possesses four bright infrared active modes. The ground and first excited states of each mode form the one-qubit computational basis set. Two approaches are proposed for the realization of the full addition. In the first one, we optimize a pulse that implements directly the entire addition by a single unitary transformation. In the second one, we decompose the full addition in elementary quantum gates, following a scheme proposed by Vedral et al. [Phys. Rev. A 54, 147 (1996)]. Four elementary quantum gates are necessary, two two-qubit CNOT gates (controlled NOT) and two three-qubit TOFFOLI gates (controlled-controlled NOT). All the logic operations consist in one-qubit flip. The logic implementation is therefore quasiclassical and the readout is based on a population analysis of the vibrational modes that does not take the phases into account. The fields are optimized by the multitarget extension of the optimal control theory involving all the transformations among the 24 qubit states. A single cycle of addition without considering the preparation or the measure or copy of the result can be carried out in a very competitive time, on a picosecond time scale. [ABSTRACT FROM AUTHOR]

The formalism of the resonance states is used to derive approximate expressions of the unimolecular law of decay resulting from a specific excitation. These expressions contain no cross terms and wash out the quantum interferences. We propose a method to relate them to an experimentally observable quantity, viz., the autocorrelation function C(t) obtained as the Fourier transform of a spectral profile, which is available even when the spectrum is poorly resolved. For a specific excitation, the exact initial rate of decay (valid up to the dephasing time T1) is equal to the initial slope of |C(t)|2. The subsequent time evolution can be obtained by averaging |C(t)|2 over its oscillations. This generates a function |C(t)|2av whose area (from time T1 onwards) is directly related to an average decay lifetime. At times t>T1, a good approximation to the average decay curve Pav(t) can be derived by multiplying |C(t)|2av by an appropriate constant. The method is exemplified on various diatomic and triatomic models. As an application to a real system, we study the B 2B2 state of H2O+ which is coupled to the A 2A1 state via a conical intersection. State B is found to undergo an ultrafast intramolecular relaxation with a lifetime of (1.6±0.2) 10-14 s. [ABSTRACT FROM AUTHOR]

We theoretically investigated the implementation of universal quantum gates in hyperfine levels of ultracold heteronuclear polar molecules in their lowest rotational manifolds. Quantum bits are manipulated by microwave pulses, taking advantage of the strong state mixing generated by the hyperfine interactions. Gate operations are either driven by a sequence of Gaussian pulses or by a pulse shaped by optimal control theory. Alkaline molecules of experimental interest are considered. We show that high fidelity gates can be driven by microsecond pulses. The richness of the energy structure and the state mixing offer promising perspectives for the manipulation of a large number of qubits. [ABSTRACT FROM AUTHOR]

Wave packet simulations using ab initio potential energy surfaces (PES) have been developed within the framework of the constrained Hamiltonian methodology. The approach is presented with the example of bromoacetyl chloride photodissociation. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [ABSTRACT FROM AUTHOR]

We simulate the implementation of a 3-qubit quantum Fourier transform gate in the hyperfine levels of ultracold polar alkali dimers in their first two lowest rotational levels. The chosen dimer is 41K87Rb supposed to be trapped in an optical lattice. The hyperfine levels are split by a static magnetic field. The pulses operating in the microwave domain are obtained by optimal control theory. We revisit the problem of phase control in information processing. We compare the efficiency of two optimal fields. The first one is obtained from a functional based on the average of the transition probabilities for each computational basis state but constrained by a supplementary transformation to enforce phase alignment. The second is obtained from a functional constructed on the phase sensitive fidelity involving the sum of the transition amplitudes without any supplementary constrain. [ABSTRACT FROM AUTHOR]