Composite natural orbitals for configuration interaction method

Abstract

A new method of constructing approximate natural orbitals (NO's) is proposed. A system can usually be regarded as consisting of fragments. The approximate NO's of the entire system are constructed from the NO's of fragments in their ground states. These orbitals are expected to be useful in configuration interaction (CI) calculations of a large system where orbital truncation is necessary. The usefulness of these approximate NO's, which are called composite NO's (CNO's), is demonstrated on C4H6. This molecule may be regarded as a combination of two fragments i.e., C2H4's. Excitation energies calculated by single and double excitation CI with the truncated CNO's (14σ, 7π correlating orbitals) agree reasonably well with those calculated with a full orbital set (37σ, 12π correlating orbitals), while the truncated SCFMO's of the same size give disastrous excitation energies.