Surface Hopping Dynamics on Vibronic Coupling Models.

Abstract

ConspectusThe simulation of photoinduced non-adiabatic dynamics is of great relevance in many scientific disciplines, ranging from physics and materials science to chemistry and biology. Upon light irradiation, different relaxation processes take place in which electronic and nuclear motion are intimately coupled. These are best described by the time-dependent molecular Schrödinger equation, but its solution poses fundamental practical challenges to contemporary theoretical chemistry. Two widely used and complementary approaches to this problem are multiconfigurational time-dependent Hartree (MCTDH) and trajectory surface hopping (SH). MCTDH is an accurate fully quantum-mechanical technique but often is feasible only in reduced dimensionality, in combination with approximate vibronic coupling (VC) Hamiltonians, or both (i.e., reduced-dimensional VC potentials). In contrast, SH is a quantum–classical technique that neglects most nuclear quantum effects but allows nuclear dynamics in full dimensionality by calculating potential energy surfaces on the fly. If nuclear quantum effects do not play a central role and a linear VC (LVC) Hamiltonian is appropriate—e.g., for stiff molecules that generally keep their conformation in the excited state—then it seems advantageous to combine the efficient LVC and SH techniques. In this Account, we describe how surface hopping based on an LVC Hamiltonian (SH/LVC)—as recently implemented in the SHARC surface hopping package—can provide an economical and automated approach to simulate non-adiabatic dynamics. First, we illustrate the potential of SH/LVC in a number of showcases, including intersystem crossing in SO2, intra-Rydberg dynamics in acetone, and several photophysical studies on large transition-metal complexes, which would be much more demanding or impossible to perform with other methods. While all of the applications provide very useful insights into light-induced phenomena, they also hint at difficulties faced by the SH/LVC methodology that need to be addressed in the future. Second, we contend that the SH/LVC approach can be useful to benchmark SH itself. By the use of the same (LVC) potentials as MCTDH calculations have employed for decades and by relying on the efficiency of SH/LVC, it is possible to directly compare multiple SH test calculations with a MCTDH reference and ponder the accuracy of various correction algorithms behind the SH methodology, such as decoherence corrections or momentum rescaling schemes. Third, we demonstrate how the efficiency of SH/LVC can also be exploited to identify essential nuclear and electronic degrees of freedom to be employed in more accurate MCTDH calculations. Lastly, we show that SH/LVC is able to advance the development of SH protocols that can describe nuclear dynamics including explicit laser fields—a very challenging endeavor for trajectory-based schemes. To end, this Account compiles the typical costs of contemporary SH simulations, evidencing the great advantages of using parametrized potentials. The LVC model is a sleeping beauty that, kissed by SH, is fueling the field of excited-state molecular dynamics. We hope that this Account will stimulate future research in this direction, leveraging the advantages of the SH/VC schemes to larger extents and extending their applicability to uncharted territories.