Chuan-Cun Shu

Phase-only shaped laser pulses in optimal control theory: Application to indirect photofragmentation dynamics in the weak-field limit

We implement phase-only shaped laser pulses within quantum optimal control theory for laser-molecule interaction. This approach is applied to the indirect photofragmentation dynamics of NaI in the weak-field limit. It is shown that optimized phase-modulated pulses with a fixed frequency distribution can substantially modify transient dissociation probabilities as well as the momentum distribution associated with the relative motion of Na and I.

Field-free molecular orientation with terahertz few-cycle pulses

We demonstrate theoretically an efficient field-free orientation in LiH and LiCl driven by available terahertz few-cycle pulses (TFCPs). Exact results by numerically solving the time-dependent Schrodinger equation including the vibrational and rotational degrees of freedom are compared to the rigid-rotor approximation (RRA) as well as to the impulsive approximation (IA), and the effect of rotational-vibrational coupling on the both RRA and IA is examined in detail. We find that the current available TFCPs may overcome the technical limitation of terahertz half-cycle pulse for enhancing the field-free molecular orientation.

Coherent control of indirect photofragmentation in the weak-field limit: Control of transient fragment distributions

We demonstrate theoretically that laser-induced coherent quantum interference control of asymptotic states of dissociating molecules is possible--even in the (one-photon) weak-field limit starting from a single vibrational eigenstate--when resonances are in play. This is illustrated for the NaI molecule, where it is shown that the probability of observing atomic fragments as well as the distribution of their relative momenta can be changed by a phase modulated pulse with a fixed bandwidth. This type of control is restricted to finite times during the indirect fragmentation.

Optimal control of charge transfer for slow H+ + D collisions with shaped laser pulses.

We show that optimally shaped laser pulses can beneficially influence charge transfer in slow H(+)+D collisions. Time-dependent wave packet optimal control simulations are performed based on a two-state adiabatic Hamiltonian. Optimal control is performed using either an adaptive or a fixed target to obtain the desired laser control field. In the adaptive target scheme, the target state is updated according to the renormalized fragmentary yield in the exit channel throughout the optimization process. In the fixed target scheme, the target state in the exit channel is a normalized outgoing Gaussian wave packet located at a large internuclear separation. Both approaches produced excellent optimal outcomes, far exceeding that achieved in the field-free collisional charge transfer. The adaptive target scheme proves to be more efficient, and often with complex final wave packet. In contrast, the fixed target scheme, although more slowly convergent, is found to produce high fidelity for the desired target wave packet. The control mechanism in both cases utilizes bound vibrational states of the transient HD(+) complex.

A theoretical investigation of the feasibility of Tannor-Rice type control: Application to selective bond breakage in gas-phase dihalomethanes

Within the B̃ absorption band of CH(2)BrCl, we theoretically analyze the laser-induced control of the Br/Cl branching ratio, Br + CH(2)Cl ← CH(2)BrCl → CH(2)Br + Cl, with CH(2)BrCl initially in its vibrational ground state. For weak-field excitation, the Br/Cl branching ratio increases as a function of wavelength, however, for wavelengths below 180 nm the branching ratio cannot be made smaller than 0.4. Using optimal control theory, we show that the branching ratio can be made significantly less than 0.4, only when very strong fields are employed. Thus, the present work strongly suggests that a Tannor-Rice type laser control mechanism for selective bond breakage in CH(2)BrCl cannot take place without accompanying photoionization.

Identifying Strong-Field Effects in Indirect Photofragmentation Reactions.

Exploring molecular breakup processes induced by light-matter interactions has both fundamental and practical implications. However, it remains a challenge to elucidate the underlying reaction mechanism in the strong field regime, where the potentials of the reactant are modified dramatically. Here we perform a theoretical analysis combined with a time-dependent wavepacket calculation to show how a strong ultrafast laser field affects the photofragment products. As an example, we examine the photochemical reaction of breaking up the molecule NaI into the neutral atoms Na and I, which due to inherent nonadiabatic couplings are indirectly formed in a stepwise fashion via the reaction intermediate NaI*. By analyzing the angular dependencies of fragment distributions, we are able to identify the reaction intermediate NaI* from the weak to the strong field-induced nonadiabatic regimes. Furthermore, the energy levels of NaI* can be extracted from the quantum interference patterns of the transient photofragment momentum distribution.

Attosecond Dynamics of Molecular Electronic Ring Currents

Ultrafast charge migration is of fundamental importance to photoinduced chemical reactions. However, exploring such a quantum dynamical process requires demanding spatial and temporal resolutions. We show how electronic coherence dynamics induced in molecules by a circularly polarized UV pulse can be tracked by using a time-delayed circularly polarized attosecond X-ray pulse. The X-ray probe spectra retrieve an image at different time delays, encoding instantaneous pump-induced circular charge migration information on an attosecond time scale. A time-dependent ultrafast electronic coherence associated with the periodical circular ring currents shows a strong dependence on the helicity of the UV pulse, which may provide a direct approach to access and control the electronic quantum coherence dynamics in photophysical and photochemical reactions in real time.

The carrier-envelope phase dependence of above threshold dissociation for HD+ driven by the modulated laser field

The dependence of above threshold dissociation (ATD) dynamics of HD+ on the carrier-envelope phase (CEP) of the modulated laser pulse is studied theoretically by numerically solving the time-dependent Schrodinger equation including the molecular vibrational and rotational degrees of freedom. The energy-dependent spectra of dissociated fragments, resulting from the ATD, are calculated by using an asymptotic-flow expression in the momentum space. We find that the ATD spectra are dependent on the CEP , indicating that the ATD dynamics can be efficiently controlled by varying the CEP . Moreover, we examine the ATD dynamics for different intensities and CEPs of the modulated laser pulse. The ATD dynamics process is interpreted in terms of the light-dressed potential.

Resonance-enhanced above-threshold ionization of polar molecules induced by ultrashort laser pulses

The dynamics of resonance-enhanced above-threshold ionization (REATI) is theoretically investigated for polar molecules exposed to ultrashort laser pulses. Numerical calculations are performed for a three-state NaK molecule including two bound states and an ionization continuum. It is found that, due to the effect of a permanent dipole moment, an enhancement of ATI can be achieved. The visible Autler–Townes (AT) splitting of the ATI spectrum induced by a sufficiently rapid Rabi oscillation is observed. Moreover, the effect of other states on the REATI process is discussed based on a four-state REATI model including three bound states and an ionization continuum.

Determination of the phase of terahertz few-cycle laser pulses

We propose an approach to determine the carrier-envelope phase (CEP) of a terahertz few-cycle pulse by observing the field-free molecular orientation. We find that the degree of orientation sensitively depends on the CEP, providing a new route for measuring the CEP without phase ambiguity. By taking advantage of the field-free molecular orientation, an important effect of the CEP drift caused by the dephasing of the generating medium on the accurate measurement of the CEP value is eliminated.