Laser-driven Molecules Research Articles

Non-Markovian dynamics of the electronic subsystem in a laser-driven molecule: Characterization and connections with electronic-vibrational entanglement and electronic coherence

Non-Markovian quantum evolution of the electronic subsystem in a laser-driven molecule is characterized through the appearance of negative decoherence rates in the canonical form of the electronic master equation. For a driven molecular system described in a bipartite Hilbert space $\mathcal{H}={\mathcal{H}}_{el}⨂{\mathcal{H}}_{\mathrm{vib}}$ of dimension $2\ifmmode\times\else\texttimes\fi{}{N}_{v}$, we derive the canonical form of the electronic master equation, deducing the canonical measures of non-Markovianity and the Bloch volume of accessible states. We find that one of the decoherence rates is always negative, accounting for the inherent non-Markovian character of the electronic evolution in the vibrational environment. Enhanced non-Markovian behavior, characterized by two negative decoherence rates, appears if there is a coupling between the electronic states $g,\phantom{\rule{0.16em}{0ex}}e$, such that the evolution of the electronic populations obeys $d({P}_{g}{P}_{e})/dt>0$. Non-Markovianity of the electronic evolution is analyzed in relation to temporal behaviors of the electronic-vibrational entanglement and electronic coherence, showing that enhanced non-Markovian behavior accompanies entanglement increase. Taking as an example the coupling of two electronic states by a laser pulse in the ${\mathrm{Cs}}_{2}$ molecule, we analyze non-Markovian dynamics under laser pulses of various strengths, finding that the weaker pulse stimulates the bigger amount of non-Markovianity. Our results show that increase of the electronic-vibrational entanglement over a time interval is correlated to the growth of the total amount of non-Markovianity calculated over the same interval using canonical measures and connected with the increase of the Bloch volume. After the pulse, non-Markovian behavior is correlated to electronic coherence, such that vibrational motion in the electronic potentials which diminishes the nuclear overlap, implicitly increasing the linear entropy of entanglement, brings a memory character to dynamics.

Time-dependent quantum chemistry of laser driven many-electron molecules.

A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied to calculate the detailed, sub-cycle electronic dynamics of BeH2, treated in a 3-21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10(15) W/cm(2)), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.

Nuclear Reaction Induced by Carrier-Envelope-Phase Controlled Proton Recollision in a Laser-Driven Molecule

Nuclear reactions induced by proton recollision with a nearby nucleus are studied in a setup where a neutral molecule is exposed to an extremely intense, few-cycle laser pulse. At the rising edge of the laser pulse, all electrons in the molecule are first ejected by field ionization, resulting in a molecule consisting of the bare nuclei only. A proton in the bare molecule is subsequently accelerated by the laser field in such a way that it recollides with a nearby, heavier nucleus, with a kinetic energy high enough to induce a nuclear reaction. As a specific example, the probability of triggering the (15)N(p,α)(12)C reaction by exposing either a (15)NH molecule or a (15)NH3 molecule to an intense laser pulse is calculated using the classical trajectory Monte Carlo method. We show that the proton recollision process can be controlled both by varying the carrier-envelope phase of the laser field and by the degree of molecular orientation. We also find that the magnetic field of the laser pulse plays a crucial role in the recollision dynamics.

Alignment effects in two-photon double ionization of H2in femtosecond xuv laser pulses

Triple-differential cross sections for two-photon double ionization of the aligned hydrogen molecule at the equilibrium distance are presented for a central photon energy of 30 eV. The temporal response of the laser-driven molecule is investigated by solving the time-dependent Schr\"odinger equation in full dimensionality using two-center elliptical coordinates and a finite-element discrete-variable-representation approach. The molecular orientation is found to have a strong effect on the emission modes of the two correlated photoelectrons. This molecular effect is most noticeable when the molecular axis and the laser polarization vector are oriented parallel to each other. For intermediate cases between the parallel and perpendicular geometries, the dominant emission modes for two-electron ejection oscillate between those for the two extreme cases. The contributions from different ionization channels are also analyzed in detail. Depending on the emission direction of the reference electron, the interference contributions from the various channels can be constructive or destructive at small alignment angles, while they always contribute constructively to the triple-differential cross sections near the perpendicular geometry.

Nonvariational time-dependent multiconfiguration self-consistent field equations for electronic dynamics in laser-driven molecules

A time-dependent multiconfiguration self-consistent field (TDMCSCF) scheme is developed to describe the time-resolved electron dynamics of a laser-driven many-electron atomic or molecular system, starting directly from the time-dependent Schrodinger equation for the system. This nonvariational formulation aims at the full exploitations of concepts, tools, and facilities of existing, well-developed quantum chemical MCSCF codes. The theory uses, in particular, a unitary representation of time-dependent configuration mixings and orbital transformations. Within a short-time, or adiabatic approximation, the TDMCSCF scheme amounts to a second-order split-operator algorithm involving generically the two noncommuting one-electron and two-electron parts of the time-dependent electronic Hamiltonian. We implement the scheme to calculate the laser-induced dynamics of the two-electron H2 molecule described within a minimal basis, and show how electron correlation is affected by the interaction of the molecule with a strong laser field.

Laser-Induced Resonance Shifts of Single Molecules Self-Coupled by a Metallic Surface

The spectral properties of single molecules placed near a metallic surface are investigated at low temperatures. Because of the high quality factor of the optical resonance, a laser-induced shift of the molecular lines is evidenced for the first time. The shift dependence on the laser excitation intensity and on the dephasing rate of the transition dipole is studied. A simple theoretical model of a laser-driven molecule self-coupled by a mirror is developed to qualitatively interpret the observations.

Erratum: Rotational master equation for cold laser-driven molecules [Phys. Rev. A 67, 063805 (2003)

Erratum: Rotational master equation for cold laser-driven molecules [Phys. Rev. A 67, 063805 (2003)

Rotational master equation for cold laser-driven molecules

The equations of motion for the molecular rotation are derived for vibrationally cold dimers that are polarized by off-resonant laser light. It is shown that, by eliminating electronic and vibrational degrees of freedom, a quantum master equation for the reduced rotational density operator can be obtained. The coherent rotational dynamics is caused by stimulated Raman transitions, whereas spontaneous Raman transitions lead to decoherence in the motion of the quantized angular momentum. As an example the molecular dynamics for the optical Kerr effect is chosen, revealing decoherence and heating of the molecular rotation.

Molecular orbitals and resonances for field-ionization of laser-driven molecules

We establish a rigorous demonstration that the quasi-static picture of molecular dynamics in intense laser fields derives from a high-order adiabatic representation associated with an approximate Lewis dynamical invariant of the laser-driven system. Qualitative changes in molecular structure as reflected in the molecular orbital compositions are discussed in this adiabatic representation, using a scheme of linear combination of field-induced (or field-conditioned) atomic orbitals. The scheme is illustrated on the specific example of an H 2O molecule prealigned in a laser field. Challenges in the quantum-chemical treatment of resonances for tunnel-ionization processes in the quasi-static picture are then identified, and elements of solutions to these problems are proposed, and illustrated on the simple one- and two-electron systems H 2 + and H 2.

Exact optical master equations for non-Markovian dephasing in small molecules

Generalized optical master equations are derived that describe extremely non-Markovian dephasing phenomena in small, laser-driven molecules. These equations are exact in the sense that no Born approximation or related approximation scheme is applied. Effects of non-Markovian dephasing on the intensity of light scattering are briefly discussed.

Quantum-mechanical study of the survival probability in laser-driven molecules: The role of diagonal and off-diagonal disorder.

Quantum-mechanical study of the survival probability in laser-driven molecules: The role of diagonal and off-diagonal disorder.

Chaotic attractor with hysteresis in laser-driven molecules

Period-doubling bifurcations into a chaotic state are found in a quantum statistical model of multiphoton excitation of a molecule when the laser field is modulated sinusoidally. This chaotic state characterizes a strange attractor coexisting with a periodic one. Interesting dynamical behavior associated with these attractors is described and practical implications of this molecular property discussed.