Journal of Physical Chemistry A, Vol.120, No.45, 9019-9027, 2016
Interaction of Helium Rydberg State Molecules with Dense Helium
The interaction potentials of the He-2* excimer, in the a(3)Sigma u(,) b(g)(3 Pi) C-3 Sigma E-g and d(3)Sigma(u) electronic states with a ground state helium atom are presented. The symmetry of the interaction potentials closely follows the excimer Rydberg electron density with pronounced shortrange minima appearing along the nodal planes of the Rydberg orbital. In such cases, a combination of the electrostatic short-range attraction combined with Pauli repulsion leads to the appearance of unusual longrange maxima in the potentials. Bosonic density functional calculations show that the 3d state excimer resides in a localized solvation bubble in dense helium at 4.5 K, with radii varying from 12.7 A at 0.1 MPa to 10.8 A at 2.4 MPa. The calculated 3d 3b pressure -induced fluorescence band shifts are in good agreement with experimental results determined by application of corona discharge. The magnitude of the spectral shifts indicate that the observed He molecules emit from dense helium whereas the corresponding fluorescence signal from the discharge zone appears quenched. This implies that fluorescence spectroscopy involving this electronic transition can only be used to probe the state of the surrounding medium rather than the discharge zone itself.