DISSIPATIVE DYNAMICS IN A CURVE-CROSSING SYSTEM - THE N-2 MOLECULE

Density matrix theory is applied to the study of environmental effects on the dynamics of vibrational degrees of freedom in coupled potential energy surfaces. For this purpose we formulate the theory in a diabatic state representation and incorporate the environment to second order of perturbation theory. As an example we study the dynamics on the coupled b'1SIGMA(u)+-c'1SIGMA(u)+ potential energy surfaces of the N2 molecule which is supposed to be immobilized in a solid state matrix. The resulting dependence of the vibrational dynamics on the coupling strength to the matrix degrees of freedom is discussed in the context of a pump probe experimental configuration. It is found that with increasing coupling strength oscillatory structures in the probe spectrum are strongly suppressed.