Electronic-Rotational Coupling in Cl–para-H2 Van der Waals Dimers

الملخص EN

We examine the interaction between an open-shell chlorine atom and a para-H2 molecule in the region of configuration space that corresponds to a weakly bound Cl–para-H2 van der Waals dimer.

By constructing and diagonalizing the Hamiltonian matrix that represents the coupled Cl atom electronic and H2 rotational degrees of freedom, we obtain one-dimensional energy curves for the Cl–para-H2 system in this region of configuration space.

We find that the dimer exhibits fairly strong electronic-rotational coupling when the Cl–H2 distance R is close to R=5.5a0; however, this coupling does not modify substantially the positions and depths of the van der Waals wells in the dimer’s E(R) curves.

An approximation in which the para-H2 fragment is treated in the strict j=0 limit thus appears to yield an accurate representation of those states of the weakly bound Cl–para-H2 dimer that correlate with j=0 H2 in the R→∞ limit.