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The Journal of Chemical Physics

A hierarchical effective mode approach to phonon-driven multilevel vibrational relaxation dynamics at surfaces

Eric W. Fischer, Michael Werther, Foudhil Bouakline, Peter Saalfrank

Published Aug 10, 2020• 8 citations
Publisher

Abstract

We discuss an efficient Hierarchical Effective Mode (HEM) representation of a high-dimensional harmonic oscillator bath, which describes phonon-driven vibrational relaxation of an adsorbate-surface system, namely, deuterium adsorbed on Si(100). Starting from the original Hamiltonian of the adsorbate-surface system, the HEM representation is constructed via iterative orthogonal transformations, which are efficiently implemented with Householder matrices. The detailed description of the HEM representation and its construction are given in the second quantization representation. The hierarchical nature of this representation allows access to the exact quantum dynamics of the adsorbate-surface system over finite time intervals, controllable via the truncation order of the hierarchy. To study the convergence properties of the effective mode representation, we solve the time-dependent Schrödinger equation of the truncated system-bath HEM Hamiltonian, with the help of the multilayer extension of the Multiconfigurational Time-Dependent Hartree (ML-MCTDH) method. The results of the HEM representation are compared with those obtained with a quantum-mechanical tier-model. The convergence of the HEM representation with respect to the truncation order of the hierarchy is discussed for different initial conditions of the adsorbate-surface system. The combination of the HEM representation with the ML-MCTDH method provides information on the time evolution of the system (adsorbate) and multiple effective modes of the bath (surface). This permits insight into mechanisms of vibration-phonon coupling of the adsorbate-surface system, as well as inter-mode couplings of the effective bath.

DOI
10.1063/5.0017716

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We discuss an efficient Hierarchical Effective Mode (HEM) representation of a high-dimensional harmonic oscillator bath, which describes phonon-driven vibrational relaxation of an adsorbate-surface system, namely, deuterium adsorbed on Si(100). Starting from the original Hamiltonian of the adsorbate-surface system, the HEM representation is constructed via iterative orthogonal transformations, which are efficiently implemented with Householder matrices. The detailed description of the HEM representation and its construction are given in the second quantization representation. The hierarchical nature of this representation allows access to the exact quantum dynamics of the adsorbate-surface system over finite time intervals, controllable via the truncation order of the hierarchy. To study the convergence properties of the effective mode representation, we solve the time-dependent Schrödinger equation of the truncated system-bath HEM Hamiltonian, with the help of the multilayer extension of the Multiconfigurational Time-Dependent Hartree (ML-MCTDH) method. The results of the HEM representation are compared with those obtained with a quantum-mechanical tier-model. The convergence of the HEM representation with respect to the truncation order of the hierarchy is discussed for different initial conditions of the adsorbate-surface system. The combination of the HEM representation with the ML-MCTDH method provides information on the time evolution of the system (adsorbate) and multiple effective modes of the bath (surface). This permits insight into mechanisms of vibration-phonon coupling of the adsorbate-surface system, as well as inter-mode couplings of the effective bath.
Modeling the dynamics of a quantum system coupled to a dissipative environment becomes particularly challenging when the system's dimensionality is too high to permit the computation of its eigenstates. This problem is addressed by introducing an eigenstate-free formalism, where the open quantum system is represented as a mixture of high-dimensional, time-dependent wave packets governed by coupled Schrödinger equations, while the environment is described by a multi-component quantum master equation. An efficient computational implementation of this formalism is presented, employing a variational mixed Gaussian/multiconfigurational time-dependent Hartree (G-MCTDH) ansatz for the wave packets and propagating the environment dynamics via hierarchical equations, truncated at the first or second level of the hierarchy. The effectiveness of the proposed methodology is demonstrated on a 61-dimensional model of phonon-driven vibrational relaxation of an adsorbate. G-MCTDH calculations on 4- and 10-dimensional reduced models, combined with truncated hierarchical equations for the mean fields, nearly quantitatively replicate the full-dimensional quantum dynamical results on vibrational relaxation while significantly reducing the computational time. This approach thus offers a promising quantum dynamical method for modeling complex system-bath interactions, where a large number of degrees of freedom must be explicitly considered.
An approach to non-Markovian system-environment dynamics is described which is based on the construction of a hierarchy of coupled effective environmental modes that is terminated by coupling the final member of the hierarchy to a Markovian bath. For an arbitrary environment, which is linearly coupled to the subsystem, the discretized spectral density is replaced by a series of approximate spectral densities involving an increasing number of effective modes. This series of approximants, which are constructed analytically in this paper, guarantees the accurate representation of the overall system-plus-bath dynamics up to increasing times. The hierarchical structure is manifested in the approximate spectral densities in the form of the imaginary part of a continued fraction similar to Mori theory. The results are described for cases where the hierarchy is truncated at the first-, second-, and third-order level. It is demonstrated that the results generated from a reduced density matrix equation of motion and large dimensional system-plus-bath wavepacket calculations are in excellent agreement. For the reduced density matrix calculations, the system and hierarchy of effective modes are treated explicitly and the effects of the bath on the final member of the hierarchy are described by the Caldeira-Leggett equation and its generalization to zero temperature.
Several techniques to solve a hierarchical set of equations of motion for propagating a reduced density matrix coupled to a thermal bath have been developed in recent years. This is either done using the path integral technique as in the original proposal by Tanimura and Kubo [J. Phys. Soc. Jpn. 58, 101 (1998)] or by the use of stochastic fields as done by Yan et al. [Chem. Phys. Lett. 395, 216 (2004)]. Based on the latter ansatz a compact derivation of the hierarchy using a decomposition of the spectral density function is given in the present contribution. The method is applied to calculate the time evolution of the reduced density matrix describing the motion in a harmonic, an anharmonic, and two coupled oscillators where each system is coupled to a thermal bath. Calculations to several orders in the system-bath coupling with two different truncations of the hierarchy are performed. The respective density matrices are used to calculate the time evolution of various system properties and the results are compared and discussed with a special focus on the convergence with respect to the truncation scheme applied.
A reduced dynamics representation is introduced which is tailored to a hierarchical, Mori-chain type representation of a bath of harmonic oscillators which are linearly coupled to a subsystem. We consider a spin-boson system where a single effective mode is constructed so as to absorb all system-environment interactions, while the residual bath modes are coupled bilinearly to the primary mode and among each other. Using a cumulant expansion of the memory kernel, correlation functions for the primary mode are obtained, which can be suitably approximated by truncated chains representing the primary-residual mode interactions. A series of reduced-dimensional bath correlation functions is thus obtained, which can be expressed as Fourier-Laplace transforms of spectral densities that are given in truncated continued-fraction form. For a master equation which is second order in the system-bath coupling, the memory kernel is re-expressed in terms of local-in-time equations involving auxiliary densities and auxiliary operators.
The improved relaxation approach of Meyer and co-workers is extended by employing the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) theory. Within this approach the trial wave function is expressed by a recursive, multilayered expansion that is the same as in a normal ML-MCTDH simulation. Calculation of an energy eigenstate then proceeds by iteratively diagonalizing the Boltzmann operator in the top layer representation using a Lanczos/Arnoldi method while relaxing the single particle functions of all layers using the ML-MCTDH imaginary time propagation. Numerical iteration is stopped until the relative energy and/or density of the target state meet the convergence criteria. The application of this multilayer improved relaxation method is illustrated by computing the energy splitting for the lowest pair of eigenstates as well as the spin observables and entanglement entropy of the spin-boson model. A large number of degrees of freedom, up to 10,000 bath modes, can be treated, and thus the appropriate phase transition at a critical system-bath coupling strength may be predicted via appropriate extrapolations.
We investigate the effect of inter-mode coupling on the vibrational relaxation dynamics of molecules in weak dissipative environments. The simulations are performed within the reduced density matrix formalism in the Markovian regime, assuming a Lindblad form for the system-bath interaction. The prototypical two-dimensional model system representing two CO molecules approaching a Cu(100) surface is adapted from an ab initio potential, while the diatom-diatom vibrational coupling strength is systematically varied. In the weak system-bath coupling limit and at low temperatures, only first order non-adiabatic uni-modal coupling terms contribute to surface-mediated vibrational relaxation. Since dissipative dynamics is non-unitary, the choice of representation will affect the evolution of the reduced density matrix. Two alternative representations for computing the relaxation rates and the associated operators are thus compared: the fully coupled spectral basis, and a factorizable ansatz. The former is well-established and serves as a benchmark for the solution of Liouville-von Neumann equation. In the latter, a contracted grid basis of potential-optimized discrete variable representation is tailored to incorporate most of the inter-mode coupling, while the Lindblad operators are represented as tensor products of one-dimensional operators, for consistency. This procedure results in a marked reduction of the grid size and in a much more advantageous scaling of the computational cost with respect to the increase of the dimensionality of the system. The factorizable method is found to provide an accurate description of the dissipative quantum dynamics of the model system, specifically of the time evolution of the state populations and of the probability density distribution of the molecular wave packet. The influence of intra-molecular vibrational energy redistribution appears to be properly taken into account by the new model on the whole range of coupling strengths. It demontrates that most of the mode mixing during relaxation is due to the potential part of the Hamiltonian and not to the coupling among relaxation operators.