Triplet excitons in small helium clusters

P. Nijjar, A. I. Krylov, O. Prezhdo, A. Vilesov, and C. Wittig
J. Phys. Chem. A  123, 6113 – 6112 (2019)

An electron traveling through liquid helium with sufficient kinetic energy can create a low-lying triplet exciton via inelastic scattering. Accompanying repulsion between the exciton and nearby atoms results in bubble formation. That is not all, however. Repulsion compresses an "incipient He₂^* exciton," pushing it into a region where an He₂^* moiety commences evolution toward its potential energy minimum. The above picture follows from ab initio calculations of the two lowest adiabatic potential energy surfaces for collinear 3-atom systems, and dynamics studies launched on the lowest adiabat that calculate said surface on the fly. The timescale for launching trajectories toward the He₂^* moiety is significantly shorter than the timescale for pushing helium away from the exciton in large systems, making results with 3 atoms relevant to liquid helium. This explains how He₂^* might be created in the aftermath of electron-impact excitation of He^*. Interplay between the lowest adiabats is discussed, underscoring the importance of non-adiabatic processes in such systems. Results with 8-atom systems further illustrate the critical role of non-adiabatic transitions.

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