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Extending the Shin-Metiu two-electron Hamiltonian, we construct a new Hamiltonian with effective singlet-triplet couplings. The Born-Oppenheimer electronic potentials and couplings are obtained for different parameters, and the laser-free dynamics is calculated with the full Hamiltonian and in the adiabatic limit. We compare the dynamics of the system using nuclear wave packets for different numbers of Born-Oppenheimer potentials and vibronic wave packets on a full 3-dimensional (two electron coordinates plus one nuclear coordinate) grid. Using strong fields, we show that it is possible to dynamically lock the spin state of the system by decoupling the singlet-triplet transition via a nonresonant dynamic Stark effect in the adiabatic limit. Although a similar spin-locking mechanism is observed in the dynamics of vibronic wave packets, multiphoton ionization cannot be neglected leading to the breakdown of the control scheme.

Nonadiabatic ab initio molecular dynamics (MD) including spin-orbit coupling (SOC) and laser fields is investigated as a general tool for studies of excited-state processes. Up to now, SOCs are not included in standard ab initio MD packages. Therefore, transitions to triplet states cannot be treated in a straightforward way. Nevertheless, triplet states play an important role in a large variety of systems and can now be treated within the given framework. The laser interaction is treated on a non-perturbative level that allows nonlinear effects like strong Stark shifts to be considered. As MD allows for the handling of many atoms, the interplay between triplet and singlet states of large molecular systems will be accessible. In order to test the method, IBr is taken as a model system, where SOC plays a crucial role for the shape of the potential curves and thus the dynamics. Moreover, the influence of the nonresonant dynamic Stark effect is considered. The latter is capable of controlling reaction barriers by electric fields in time-reversible conditions, and thus a control laser using this effect acts like a photonic catalyst. In the IBr molecule, the branching ratio at an avoided crossing, which arises from SOC, can be influenced.

We theoretically investigate the photon-echo spectroscopy of coupled electron-nuclear quantum dynamics. Two situations are treated. In the first case, the Born-Oppenheimer (adiabatic) approximation holds. It is then possible to interpret the two-dimensional (2D) spectra in terms of vibrational motion taking place in different electronic states. In particular, pure vibrational coherences which are related to oscillations in the time-dependent third-order polarization can be identified. This concept fails in the second case, where strong non-adiabatic coupling leads to the breakdown of the Born-Oppenheimer-approximation. Then, the 2D-spectra reveal a complicated vibronic structure and vibrational coherences cannot be disentangled from the electronic motion. [ABSTRACT FROM AUTHOR]

The enhancing and inhibition of population transfer via a conical intersection is demonstrated with quantum model calculations on the 1,1-difluoroethylene system. Averaged loss-gain strategies are achieved using strong laser pulses, which either trap the wave packet in the excited state, or accelerate the wave packet in the vicinity of the conical intersection. [ABSTRACT FROM AUTHOR]

Optical enantiomers are proposed to encode molecular two-qubit information processing. Using sequences of pairs of nonresonant optimally polarized pulses, different schemes to implement quantum gates, and to prepare entangled states, are described. We discuss the role of the entanglement phase and the robustness of the pulse sequences which depend on the area theorem. Finally, possible scenarios to generalize the schemes to n-qubit systems are suggested. [ABSTRACT FROM AUTHOR]

The influence of laser noise on the dynamics of simple quantum systems is analyzed. An anharmonic ladder is chosen for illustration and several pulses are obtained that optimize the yield of a quantum transition by constraining the laser parameters. The following models of laser noise are introduced: Amplitude white noise, phase white noise, frequency white noise and shot-to-shot static noise in the different pulse parameters. It is shown that the optimal pulses are robust to white amplitude noise, since the system acts as a dynamical filter. White phase noise affects the optimal pulses in a similar way by reducing the pulse area. This effect can be easily compensated for by pulse amplitude rescaling, up to a high level of noise. White frequency noise reduces the pulse area and induces spectral broadening, more strongly affecting the high frequency components. It can be partially compensated for by amplitude rescaling. The effects of static noise in the parameters cannot be easily corrected. It is shown that optimal pulses that drive n-photon transitions become more sensitive to noise in the amplitude and less sensitive to noise in the frequency as n increases. The effects of noise in the relative phase rapidly become constant for a large number of interfering pathways. [ABSTRACT FROM AUTHOR]

We consider the creation of the maximum Raman coherence in the six-level Λ system using optimal control theory. Optimal fields are designed for different initial conditions, resonant, and off-resonant, using the Krotov method including a reference field into the cost functional. Suppression of the population transfer to the intermediate level is achieved via an additional functional constraint which depends on the system dynamics. We demonstrate that the spectrum of the optimised fields has major contribution from the corresponding resonant frequencies independently of the choice of carrier frequency of the initial guess field. We also indicate that the pulse train emerges as a solution of the control problem of coherence optimisation in multi-level quantum systems. [ABSTRACT FROM PUBLISHER]

The dynamics of molecules under strong laser pulses is characterized by large Stark effects that modify and reshape the electronic potentials, known as laser-induced potentials (LIPs). If the time scale of the interaction is slow enough that the nuclear positions can adapt to these externally driven changes, the dynamics proceeds by adiabatic following, where the nuclei gain very little kinetic energy during the process. In this regime we show that the molecular dynamics can be simulated quite accurately by a semiclassical surface-hopping scheme formulated in the adiabatic representation. The nuclear motion is then influenced by the gradients of the laser-modified potentials, and nonadiabatic couplings are seen as transitions between the LIPs. As an example, we simulate the process of adiabatic passage by light induced potentials in Na2using the surface-hopping technique both in the diabatic representation based on molecular potentials and in the adiabatic representation based on LIPs, showing how the choice of the representation is crucial in reproducing the results obtained by exact quantum dynamical calculations. [ABSTRACT FROM AUTHOR]