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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. [ABSTRACT FROM AUTHOR]

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. The scheme can be used to deform the bond during the laser excitation to an arbitrary large and constant value, or to allow slow time-dependent bond elongations. Additionally, the scheme can be used to prepare highly excited vibrational wave packets in the ground potential after the pulse is switched off, at the expense of losing some population that dissociates. These wave packets are initially localized at the outer well of the potential, at energies controllable by the excitation process. [ABSTRACT FROM AUTHOR]

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 τc. In the adiabatic regime the dynamics is fully time-reversible. The amplitude of the internuclear oscillation is controlled by the pulse frequency ω(t), while τc determines the duration (or period) of the bond oscillation. In the presence of efficient dipole coupling, the bandwidth of the pulse is the main constraint to the maximum bond stretch that can be obtained. Before the onset of the adiabatic regime the dynamics are more complex, showing dispersion of the vibrational wave packet and anharmonic deformation of the bond. However, the nonadiabatic effects are mostly canceled and full revivals are observed at certain multiples of τc. [ABSTRACT FROM AUTHOR]

In this work we show how to control the photodissociation of a diatomic molecule in the frame of light-induced potentials for different shapes of the transition dipole moments. A sequence of a half-cycle or control pulse and a delayed pump pulse is used for achieving state-selective photodissociation with high yields. The effect of the control is to shift the photodissociation bands to higher frequencies. It is also possible to dissociate the molecule in a superposition of electronic states of the fragments, even when the photodissociation bands corresponding to the different electronic states of the products are largely separated. In this case one needs to engineer the sequence delaying the half-cycle pulse after the pump pulse and additionally turning off rapidly the control pulse. Depending on the shape of the dipole functions the duration of the pulses in the sequence must be constrained to shorter times as well. Finally we show that the control scheme affects the velocity of the fragments. Although broad kinetic energy distributions are always obtained when the half-cycle pulse is short, if the Stark effect implies a blueshifting in the energy of the electronic states, the distribution of the relative speed of the fragments will be redshifted. [ABSTRACT FROM AUTHOR]

We study the photodissociation of ICl- under moderately strong (TW/cm2) and short (below picosecond) laser pulses. Using a single resonant pump pulse, the photodissociation spectra shows two barely overlapping bands corresponding to Frank–Condon excitation and dissociation in two electronic states. By adding a nonresonant stronger control pulse we show that (1) the photodissociation bands can be blueshifted and (2) the asymptotic state of the fragments depends on the chosen pulse sequence. If the pump pulse precedes the control pulse or the control pulse straddles the pump pulse, the outgoing wave packet has components in the two dissociation channels, whereas if the control pulse precedes the pump pulse, the photodissociation proceeds selectively in a single channel. [ABSTRACT FROM AUTHOR]

Selective population transfer in electronic states of dissociative molecular systems is illustrated by adopting a control scheme based on Stark-chirped rapid adiabatic passage (SCRAP). In contrast to the discrete N-level system, dynamical Stark shift is induced in a more complex manner in the molecular electronic states. Wavepacket dynamics on the light-induced potentials, which are determined by the detuning of the pump pulse, can be controlled by additional Stark pulse in the SCRAP scheme. Complete population transfer can be achieved by either lowering the energy barrier along the adiabatic passage or placing the initial wavepacket on a well-defined dressed state suitable for the control. The determination of the pulse sequence is sufficient for controlling population transfer to the target state. [ABSTRACT FROM AUTHOR]

The free motion of a nonstationary vibrational wave packet in an electronic potential is a source of interesting quantum properties. In this work we propose an iterative scheme that allows continuous stretching and squeezing of a wave packet in the ground or in an excited electronic state, by switching the wave function between both potentials with π pulses at certain times. Using a simple model of displaced harmonic oscillators and delta pulses, we derive the analytical solution and the conditions for its possible implementation and optimization in different molecules and electronic states. We show that the main constraining parameter is the pulse bandwidth. Although in principle the degree of squeezing (or stretching) is not bounded, the physical resources increase quadratically with the number of iterations, while the achieved squeezing only increases linearly. [ABSTRACT FROM AUTHOR]

Strong pulse sequences can be used to control the position and width of the molecular wave packet. In this paper we propose a new scheme to maximally compress the wave packet in a quasistatic way by freezing it at a peculiar adiabatic potential shaped by two laser pulses. The dynamic principles of the scheme and the characteristic effect of the different control parameters are presented and analyzed. We use two different molecular models, electronic potentials modeled by harmonic oscillators, with the same force constants, and the Na2 dimer, to show the typical yield that can be obtained in compressing the initial (minimum width) molecular wave function. [ABSTRACT FROM AUTHOR]

We study different schemes that allow laser controlled adiabatic manipulation of the bond in diatomic molecules by using sequences of nonresonant time-delayed chirped pulses. The schemes rely on adiabatic passage of the vibrational wave packet by laser-induced potential shaping from the ground electronic state to a laser-stabilized dissociative electronic state by two-photon absorption. The degree of control that is possible over the position (bond length) and width (bond spread) of the vibrational wave packet is compared for the different schemes. The dynamics is analyzed detailing the role of the different control knobs and the conditions that allow or break the adiabatic passage. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In this paper we propose a new method to manipulate bond lengths in molecules. The scheme uses strong fields that prepare an artificial potential with the desired equilibrium bond length, by controlling the mixing of electronic configurations, and finds an adiabatic path that connects the initial state with the laser created potential. As an illustration, we show that it is possible to control the bond length of a diatomic molecule by directly coupling the ground state and a dissociative potential, with the aid of a second excited bound potential. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We study the dynamics of two-photon nonresonant electronic excitation of diatomic molecules driven by chirped pulses. While the majority of the experimental results address the role of the chirp for fixed pulse bandwidth, we analyze the possibility of selective excitation for fixed time, as a function of the pulse bandwidth, depending on the sign of the chirp. With strong picosecond pulses and positive chirp it is shown that the dynamics always prepare the molecule in the ground vibrational level of the excited electronic state. The robustness of the dynamics inherits the properties of an effective Landau -- Zener crossing. For negative chirp the final state is very sensitive to the specific pulse bandwidth. The dynamics of the system follow a complex convoluted behavior, and the final state alternates between low vibrational levels of the excited electronic state and excited vibrational levels of the ground potential, which become increasingly more excited with increasing bandwidth. The final electronic populations follow a double-period oscillatory behavior. We present a model based on sequential independent crossings which correlates the long-oscillation period with changes in the final vibrational state selected. We show that the short-oscillation period is related with nonadiabatic effects that give rise to fast dynamic Rabi flipping between the electronic states, providing only information of the field -- molecule effective coupling. Although the short-oscillation period partially masks the expected results of the final populations, we show that it is still possible to retrieve information from the long-oscillation period regarding the frequencies of the electronic potentials. In order to do so, or in order to control the outcome of the dynamics, it is necessary to perform experiments scanning very different pulse bandwidths, and we propose a possible experimental implementation. All the numerical results of the paper are calculated for a model of the... [ABSTRACT FROM AUTHOR]

A new method for the selective excitation of diatomic molecules in single vibrational states on excited electronic potentials by two-photon absorption is proposed. The method implies the use of two chirped strong pulse lasers detuned from the optical transition to an intermediate electronic state. We show under what scenarios the method is successful on the time-energy scale in which the pulses operate. They involved a long-time (nanosecond) weak-field regime and a short-time (picosecond) strong-field regime. The adiabatic representation in terms of energy levels or in terms of light-induced potentials is used to interpret the physical mechanism of the excitation. The efficiency and robustness of the scheme are demonstrated by the excitation of the ground vibrational state of the [sup 1]Σ[sub g](4s) electronic potential of the Na[sub 2] molecule. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We study the photodissociation of ICl(-) under moderately strong (TW/cm(2)) and short (below picosecond) laser pulses. Using a single resonant pump pulse, the photodissociation spectra shows two barely overlapping bands corresponding to Frank-Condon excitation and dissociation in two electronic states. By adding a nonresonant stronger control pulse we show that (1) the photodissociation bands can be blueshifted and (2) the asymptotic state of the fragments depends on the chosen pulse sequence. If the pump pulse precedes the control pulse or the control pulse straddles the pump pulse, the outgoing wave packet has components in the two dissociation channels, whereas if the control pulse precedes the pump pulse, the photodissociation proceeds selectively in a single channel.

Selective population transfer in electronic states of dissociative molecular systems is illustrated by adopting a control scheme based on Stark-chirped rapid adiabatic passage (SCRAP). In contrast to the discrete N-level system, dynamical Stark shift is induced in a more complex manner in the molecular electronic states. Wavepacket dynamics on the light-induced potentials, which are determined by the detuning of the pump pulse, can be controlled by additional Stark pulse in the SCRAP scheme. Complete population transfer can be achieved by either lowering the energy barrier along the adiabatic passage or placing the initial wavepacket on a well-defined dressed state suitable for the control. The determination of the pulse sequence is sufficient for controlling population transfer to the target state.