A global solution of the Schrodinger equation, obtained recently within the wave operator formalism for explicitly time-dependent Hamiltonians [J. Phys. A: Math. Theor. 48, 225205 (2015)], is generalized to take into account the case of multidimensional active spaces. An iterative algorithm is derived to obtain the Fourier series of the evolution operator issuing from a given multidimensional active subspace and then the effective Hamiltonian corresponding to the model space is computed and analysed as a measure of the cyclic character of the dynamics. Studies of the laser controlled dynamics of diatomic models clearly show that a multidimensional active space is required if the wavefunction escapes too far from the initial subspace. A suitable choice of the multidimensional active space, including the initial and target states, increases the cyclic character and avoids divergences occuring when one-dimensional active spaces are used. The method is also proven to be efficient in describing dissipative processes such as photodissociation.
Download