Ab initio studies of structural features not easily amenable to experiment: Part 15. The influence of solvation on molecular structure in some formic acid and carbonic acid hydrates

The completely relaxed ab initio geometries (4—21G) of a trihydrate of carbonic acid and of the monohydrates of cis and trans formic acid are compared with the corresponding unhydrated structures. The maximum structural changes caused by hydration in the free acid structures are of the order of magnitude of 0.03 Å and 3° for bond distances and bond angles, respectively. The corresponding changes in free and complexed water are 0.005 Å and 5°, respectively. The results are significant for the general problem of the transferability of gas phase molecular structures to molecules in solution and for estimates of the uncertainties in theoretical hydration energy surfaces which are generated by using fixed, monomer geometries for water and solvate molecules. Compared with the free geometries, the sum total of the structural changes in some of the systems studied corresponds to energies of several kcal mol^?1.