Dynamics near a conical intersection - A diabolical compromise for the approximations of ab initio multiple spawning

Full multiple spawning (FMS) offers an exciting framework for the development of strategies to simulate the excited-state dynamics of molecular systems. FMS proposes to depict the dynamics of nuclear wavepackets by using a growing set of traveling multidimensional Gaussian functions called trajectory basis functions (TBFs). Perhaps the most recognized method emanating from FMS is the so-called ab initio multiple spawning (AIMS). In AIMS, the couplings between TBFs - in principle exact in FMS - are approximated to allow for the on-the-fly evaluation of required electronic-structure quantities. In addition, AIMS proposes to neglect the so-called second-order nonadiabatic couplings and the diagonal Born-Oppenheimer corrections. While AIMS has been applied successfully to simulate the nonadiabatic dynamics of numerous complex molecules, the direct influence of these missing or approximated terms on the nonadiabatic dynamics when approaching and crossing a conical intersection remains unknown to date. It is also unclear how AIMS could incorporate geometric-phase effects in the vicinity of a conical intersection. In this work, we assess the performance of AIMS in describing the nonadiabatic dynamics through a conical intersection for three two-dimensional, two-state systems that mimic the excited-state dynamics of bis(methylene)adamantyl, butatriene cation, and pyrazine. The population traces and nuclear density dynamics are compared with numerically exact quantum dynamics and trajectory surface hopping results. We find that AIMS offers a qualitatively correct description of the dynamics through a conical intersection for the three model systems. However, any attempt at improving the AIMS results by accounting for the originally neglected second-order nonadiabatic contributions appears to be stymied by the hermiticity requirement of the AIMS Hamiltonian and the independent first-generation approximation.