Accurate ab initio potential energy computations for the H4 system: Tests of some analytic potential energy surfaces.

The interaction potential energy surface (PES) of H4 is of great importance for quantum chemistry, as a test case for molecule–molecule interactions. It is also required for a detailed understanding of certain astrophysical processes, namely, collisional excitation and dissociation of H2 in molecular clouds, at densities too low to be accessible experimentally. Accurate ab initio energies were computed for 6046 conformations of H4, using a multiple reference (single and) double excitation configuration interaction (MRD-CI) program. Both systematic and ‘‘random’’ errors were estimated to have an rms size of 0.6 mhartree, for a total rms error of about 0.9 mhartree (or 0.55 kcal/mol) in the final ab initio energy values. It proved possible to include in a self-consistent way ab initio energies calculated by Schwenke, bringing the number of H4 conformations to 6101. Ab initio energies were also computed for 404 conformations of H3; adding ab initio energies calculated by other authors yielded a total of 772 conformations of H3. (The H3 results, and an improved analytic PES for H3, are reported elsewhere.) Ab initio energies are tabulated in this paper only for a sample of H4 conformations; a full list of all 6101 conformations of H4 (and 772 conformations of H3 ) is available from Physics Auxiliary Publication Service (PAPS), or from the authors.The best existing analytic PESs for H4 are shown to be accurate only for pairs of H2 molecules with intermolecular separations greater than about 3 bohr (1.6 Å). High energy collisions (such as might lead to direct collisional dissociation) cannot be well represented by such surfaces. A more general analytic PES for H4 is required, which will be accurate for compact (high-energy) conformations and for conformations that cannot be subdivided into a pair of H2 molecules. Work in progress on devising such a surface (fitted to the 6101 conformations of this work) will be reported in a... [ABSTRACT FROM AUTHOR]