Real-Time Control of Electronic Motion:  Application to HD⁺

Abstract

We show that a nonstationary electron can be created in HD+ corresponding to partial electron transfer between H+ and D+. The electronic motion is introduced through nuclear motion, more specifically, through nonadiabatic curve crossing, and the electronic motion is here on the same time scale as the nuclear motion. We show that the branching ratio between the channels H + D+ and H+ + D depends on the electron distribution (i.e., where the electron “sits”) prior to the time where the bond is broken by an infrared femtosecond pulse. Thus, we controlin real-timewhich nucleus the electron will follow after the bond is broken.

Spin–orbit effects in photodissociation of sodium iodide

“…1,2,[7][8][9]12,14,16,32 The main features of the dynamics are understood and good correspondence between theory and experiment has been achieved. However, the discussion of the dissociation process and the interpretation of the experimental data have mostly centered around a two-state model of the potential curves without explicitly addressing the role of the spin-orbit interaction.…”

“…Alkali-metal halides have been the focus of attention of a number of recent experimental and theoretical investigations of quantum control of chemical reactions, 13,14,16 and an accurate description of the potential curves and spin-orbit coupling elements is essential for a quantitative comparison with experiments. A recent high-resolution continuous wave laser measurement of predissociating linewidths in NaI, for example, clearly demonstrated the need for more accurate potential energies and coupling elements.…”

Efficient method to generate time evolution of the Wigner function for open quantum systems

“…Both forms are difficult to solve and, as a result, a plethora of numerical methods for evolving the Wigner function propagation have been developed. These have involved (i) the integral form of Moyal's equation [20][21][22][23][24][25], (ii) reduction of the Moyal equation to a Boltzmann-like equation [26,27], (iii) propagation of Gaussian and coherent states [28][29][30][31], (iv) Monte Carlo schemes in which the Wigner function is contracted by averaging over stochastic trajectories of pure-states [32][33][34][35], and (v) evolving the density matrix in the coordinate representation [36,37].…”

Controlling the Electrons Provides Means for Controlling Chemistry

“…A complementary two pulse concept where creation of a nuclear and an electronic wave packet is steered by one and bond breaking by another laser pulse has been reported for HD + by Gronager et al [12] The general effect of phase on photochemical processes was discussed by Korolkov et al, [13] Levesque et al [14] and more recently by Korolkov and Weitzel. [15] Even more recent studies in our group revealed dramatic effects of the carrier envelope phase on the product branching ratio in the dissociation of DCl + ions.…”