Absolute control over the quantum yield of a photodissociation reaction mediated by nonadiabatic couplings.

Control of molecular reaction dynamics with laser pulses has been developed in the last decades. Among the different magnitudes whose control has been actively pursued, the branching ratio between different product channels constitutes the clearest signature of quantum control. In polyatomic molecules, the dynamics in the excited state is quagmired by non-adiabatic couplings, which are not directly affected by the laser, making control over the branching ratio a very demanding challenge.

Impact of Early Coherences on the Control of Ultrafast Photodissociation Reactions.

By coherent control, the yield of photodissociation reactions can be maximized, starting in a suitable superposition of vibrational states. In ultrafast processes, the interfering pathways are born from the early vibrational coherences in the ground electronic potential. We interpret their effect from a purely classical picture, in which the correlation between the initial position and momentum helps to synchronize the vibrational dynamics at the Franck-Condon window when the pulse is at its maximum intensity.

Two-qubit atomic gates: spatio-temporal control of Rydberg interaction.

By controlling the temporal and spatial features of light, we propose a novel protocol to prepare two-qubit entangling gates on atoms trapped at close distance, which could potentially speed up the operation of the gate from the sub-micro to the nanosecond scale. The protocol is robust to variations in the pulse areas and the position of the atoms, by virtue of the coherent properties of a dark state, which is used to drive the population through Rydberg states. From the time-domain perspective, the protocol generalizes the one proposed by Jaksch and coworkers [Jaksch , , 2000, , 2208], with three pulses that operate symmetrically in time, but with different pulse areas.

Circularly polarized light-induced potentials and the demise of excited states.

In the presence of strong electric fields, the excited states of single-electron molecules and molecules with large transient dipoles become unstable because of anti-alignment, the rotation of the molecular axis perpendicular to the field vector, where bond hardening is not possible. We show how to overcome this problem by using circularly polarized electromagnetic fields. Using a full quantum description of the electronic, vibrational, and rotational degrees of freedom, we characterize the excited electronic state dressed by the field and analyze its dependence on the bond length and angle and the stability of its vibro-rotational eigenstates.

Anti-alignment driven dynamics in the excited states of molecules under strong fields.

We develop two novel models of the H2+ molecule and its isotopes from which we assess quantum-mechanically and semi-classically whether the molecule anti-aligns with the field in the first excited electronic state. The results from both models allow us to predict anti-alignment dynamics even for the HD+ isotope, which possesses a permanent dipole moment. The molecule dissociates at angles perpendicular to the field polarization in both the excited and the ground electronic state, as the population is exchanged through a conical intersection.

Control defeasance by anti-alignment in the excited state.

We predict anti-alignment dynamics in the excited state of H or related homonuclear dimers in the presence of a strong field. This effect is a general indirect outcome of the strong transition dipole and large polarizabilities typically used to control or to induce alignment in the ground state. In the excited state, however, the polarizabilities have the opposite sign compared to those in the ground state, generating a torque that aligns the molecule perpendicular to the field, deeming any laser-control strategy impossible.

Halogen-atom effect on the ultrafast photodissociation dynamics of the dihalomethanes CHICl and CHBrI.

A comparative study of the ultrafast photodissociation dynamics of the dihalomethanes CH2ICl and CH2BrI has been carried out at 268 nm, around the maximum of the first absorption band, employing femtosecond velocity map ion imaging in conjunction with high level ab initio electronic structure calculations and full dimension on-the-fly trajectory calculations including surface hopping. Total translational energy distributions and angular distributions of the iodine fragments as well as reaction times for the C-I bond cleavage are presented and discussed along with the computed absorption spectra, potential energy curves and trajectories. The revealed dynamics is mainly governed by absorption to the 5A' state for CH2BrI while two dissociation pathways, through the 4A' or 5A' states, are in competition for CH2lCI.

Anomalous Rabi Oscillations in Multilevel Quantum Systems.

We show that the excitation probability of a state within a manifold of levels undergoes Rabi oscillations with the frequency determined by the energy difference between the states and not by the pulse area, for sufficiently strong pulses. The population and coherence remains in the two-level subsystem formed by the initial and target state even at Rabi frequencies exceeding the energy difference. The observed dynamics can be useful in nonlinear spectroscopy and quantum state preparation.

Geometrical Optimization Approach to Isomerization: Models and Limitations.

We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism.

Nonresonant electronic transitions induced by vibrational motion in light-induced potentials.

We find a new mechanism of electronic population inversion using strong femtosecond pulses, where the transfer is mediated by vibrational motion on a light-induced potential. The process can be achieved with a single pulse tuning its frequency to the red of the Franck-Condon window. We show the determinant role that the gradient of the transition dipole moment can play on the dynamics, and extend the method to multiphoton processes with odd number of pulses.

Protecting and accelerating adiabatic passage with time-delayed pulse sequences.

Using numerical simulations of two-photon electronic absorption with femtosecond pulses in Na2 we show that: (i) it is possible to avoid the characteristic saturation or dumped Rabi oscillations in the yield of absorption by time-delaying the laser pulses; (ii) it is possible to accelerate the onset of adiabatic passage by using the vibrational coherence starting in a wave packet; and (iii) it is possible to prepare the initial wave packet in order to achieve full state-selective transitions with broadband pulses. The findings can be used, for instance, to achieve ultrafast adiabatic passage by light-induced potentials and understand its intrinsic robustness.

State-Selective Excitation of Quantum Systems via Geometrical Optimization.

We lay out the foundations of a general method of quantum control via geometrical optimization. We apply the method to state-selective population transfer using ultrashort transform-limited pulses between manifolds of levels that may represent, e.g.

Ultrafast Population Inversion without the Strong Field Catch: The Parallel Transfer.

Quantum systems with sublevel structures, like molecules, prevent full population inversion from one manifold of sublevels to the other using ultrafast resonant pulses. We explain the mechanism by which this population transfer is blocked. We then develop a novel concept of geometric control, assuming full or partial coherent manipulation within the manifolds, and show that by preparing specific coherent superpositions in the initial manifold, full population inversion or full population blockade, that is, laser transparency, can be achieved.

Communication: Vibrational and vibronic coherences in the two dimensional spectroscopy of coupled electron-nuclear motion.

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.

Strong field laser control of photochemistry.

Strong ultrashort laser pulses have opened new avenues for the manipulation of photochemical processes like photoisomerization or photodissociation. The presence of light intense enough to reshape the potential energy surfaces may steer the dynamics of both electrons and nuclei in new directions. A controlled laser pulse, precisely defined in terms of spectrum, time and intensity, is the essential tool in this type of approach to control chemical dynamics at a microscopic level.

Control of ultrafast molecular photodissociation by laser-field-induced potentials.

Experiments aimed at understanding ultrafast molecular processes are now routine, and the notion that external laser fields can constitute an additional reagent is also well established. The possibility of externally controlling a reaction with radiation increases immensely when its intensity is sufficiently high to distort the potential energy surfaces at which chemists conceptualize reactions take place. Here we explore the transition from the weak- to the strong-field regimes of laser control for the dissociation of a polyatomic molecule, methyl iodide.

Ultrafast coherent control of giant oscillating molecular dipoles in the presence of static electric fields.

We propose a scheme to generate electric dipole moments in homonuclear molecular cations by creating, with an ultrashort pump pulse, a quantum superposition of vibrational states on electronic states strongly perturbed by very strong static electric fields. By field-induced molecular stabilization, the dipoles can reach values as large as 50 Debyes and oscillate on a time-scale comparable to that of the slow vibrational motion. We show that both the electric field and the pump pulse parameters can be used to control the amplitude and period of the oscillation, while preventing the molecule from ionizing or dissociating.

Two-pulse control of large-amplitude vibrations in H2(+).

A laser-adiabatic manipulation of the bond (LAMB) scheme using moderately intense fields is proposed to induce and control large-amplitude oscillations in nuclear wave packets. The present scheme involves an ultrashort UV pump pulse to initially create a wave packet in an excited electronic state of the hydrogen molecular ion and a low-frequency control pulse, which is switched on after a given time, leading to controllable vibrational trapping. The choice of H2(+) as the target exploits the larger dipole values that molecular ions present as the internuclear distance increases.

Quantum wave-packet dynamics in spin-coupled vibronic states.

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.

Mixed quantum-classical dynamics in the adiabatic representation to simulate molecules driven by strong laser pulses.

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.

Ultrafast control of the internuclear distance with parabolic chirped pulses.

Recently, control over the bond length of a diatomic molecule with the use of parabolic chirped pulses was predicted on the basis of numerical calculations [Chang; et al. Phys. Rev.

Laser adiabatic manipulation of the bond length of diatomic molecules with a single chirped pulse.

We propose and test numerically a scheme for controlling the bond distance in a diatomic molecule that requires the use of a single chirped pulse. The laser prepares a superposition state of both nuclear and electronic degrees of freedom, where the main character of the electronic wave function is that of an excited dissociative state. The main limitation of the scheme is the need of ultra broadband pulses, where the bandwidth must be of the order of the dissociation energy to achieve large bond elongations.

Bond lengths of diatomic molecules periodically driven by light: the p-LAMB scheme.

A laser scheme using a periodically changing frequency is used to induce oscillations of the internuclear motion, which are quantum analogs of classical vibrations in diatomic molecules. This is what we call the periodic laser adiabatic manipulation of the bond, or p-LAMB scheme. In p-LAMB, the carrier frequency of the laser must vary periodically from the blue to the red of a photodissociation band and backwards, following for instance a cosine-dependent frequency of period τ(c).