In this paper, multidimensional dissipative quantum dynamics is studied within a system–bath approach in the Markovian regime using a model Lindblad operator. We report on the implementation of a Monte Carlo wave packet algorithm in the Heidelberg version of the Multi-Configuration Time-Dependent Hartree (MCTDH) program package, which is henceforth extended to treat stochastic dissipative dynamics. The Lindblad operator is represented as a sum of products of one-dimensional operators. The new form of the operator is not restricted to the MCTDH formalism and could be used with other multidimensional quantum dynamical methods. As a benchmark system, a two-dimensional coupled oscillators model representing the internal stretch and the surface–molecule distance in the O2/Pt(111) system coupled to a Markovian bath of electron–hole-pairs is used. The simulations reveal the interplay between coherent intramolecular coupling due to anharmonic terms in the potential and incoherent relaxation due to coupling to an environment. It is found that thermalization of the system can be approximately achieved when the intramolecular coupling is weak.

In this article, we explore the dissipation dynamics of a strongly coupled multidimensional system in contact with a Markovian bath following a system-bath approach. We use in this endeavour the recently developed stochastic Multi-Configuration Time-Dependent Hartree approach within the Monte Carlo wave packet formalism [J. Chem. Phys. 156, 094109 (2022)]. The method proved to yield thermalized ensembles of wave packets when intramolecular coupling is weak. To treat strongly coupled systems, new Lindblad dissipative operators are constructed as linear combinations of the system coordinates and associated momenta. These are obtained by an unitary transformation to a normal mode representation, which reduces intermode coupling up to second order. Additionally, we use combinations of generalized raising/lowering operators to enforce the Boltzmann distribution in the dissipation operators, which yield perfect thermalization in the harmonic limit. The two ansatz are tested using a model two-dimensional hamiltonian parameterized to disentangle the effects of intramolecular potential coupling, of strong mode mixing observed in Fermi resonances, and of anharmonicity.