  Quantum reflection is a pure wave phenomena that predicts reflection of a
particle at a changing potential for cases where complete transmission occurs
classically. For a chemical bond, we find that this effect can lead to
non-classical vibrational turning points and bound states at extremely large
interatomic distances. Only recently has the existence of such ultralong-range
Rydberg molecules been demonstrated experimentally. Here, we identify a broad
range of molecular lines, most of which are shown to originate from two
different novel sources: a single-photon associated triatomic molecule formed
by a Rydberg atom and two ground state atoms and a series of excited dimer
states that are bound by a so far unexplored mechanism based on internal
quantum reflection at a steep potential drop. The properties of the Rydberg
molecules identified in this work qualify them as prototypes for a new type of
chemistry at ultracold temperatures.
