Chemistry in strong laser fields: An example from methyl iodide photodissociation

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Abstract
Time‐dependent quantum‐mechanical theories and simulations provide a clear and intuitive description of molecular processes. Due to ensuing simplification of the theory and the generally employed numerical algorithms, the vast majority of these treatments are based upon perturbation theory. Especially in light of the current level of experimental sophistication, with experiments being realized which are influenced by the spectral, temporal, and spatial shape of the laser pulse, it is important to move beyond treatments limited to weak fields or idealized δ‐function wave forms. Various methods to examine the results of high‐field simulations are presented. All of the techniques are shown to have the familiar linear response form in the weak‐field limit. In a time‐dependent framework the difference between the linear and nonlinear response expressions can be seen from expectation values over stationary versus nonstationary states. The high‐field photodissociation of methyl iodide illustrates this approach. Methyl iodide represents a physical system well suited for examining the effects of such exciting laser‐field characteristics as strength, linewidth, and frequency upon the photodissociation dynamics. Its dissociation occurs upon coupled repulsive excited electronic potential‐energy surfaces which have recently been revised to fit the most current experimental data. The effect of the surface intersection has previously been typically studied by examining the branching and the internal state distributions of the products in the two channels as a function of excitation frequency only. The collinear photodissociation dynamics is examined using a numerically exact time‐dependent quantum‐mechanical method. The equations of motion for the amplitudes upon the ground and two coupled excited electronic surfaces, explicitly incorporating the laser field, are integrated by a scheme which employs a low‐order polynomial approximation to the evolution operator. The effects of the three field characteristics upon the branching ratio and internal state distributions of the products and the spectroscopy of the process are delineated. The course of the photodissociation dynamics is shown to be affected by these characteristics. The results demonstrate the causal connections between the pulse shape and the resulting photoprocesses. Practical manifestations of strong fields (power broadening, sub‐threshold absorption, higher harmonic generation, emission shaping of the ground state, temporal development) are stressed.