New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution

Cossi, Maurizio; Scalmani, Giovanni; Rega, Nadia; Barone, Vincenzo

doi:doi:10.1063/1.1480445

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An Airy discrete variable representation basis

A new discrete variable representation (DVR) basis is presented, one that is based on Airy functions. That is, the functions of the “finite basis representation” (actually infinite in this case) are energy eigenfunctions in a constant force field. The exact matrix elements of the kinetic energy are computed. The use of the Airy DVR functions in diagonalizing a one-dimensional Hamiltonian is illustrated.© 2002 American Institute of Physics.

On the oscillator strength sums S(±1) of atoms and ions

Using rigorous relations discovered recently, the Hartree–Fock limit values of the dipole oscillator strength sums S(−1) and S(+1) are obtained for the 102 neutral atoms He through Lr, singly charged 53 cations Li+ through Cs+, and 43 stable anions H− through I− in their experimental ground states. The present results for the ionic species are the first compilation of the sums. For heavy neutral atoms, the literature S(+1) values are found to be insufficiently accurate. © 2002 American Institute...

The polarizable continuum model (PCM), used for the calculation of molecular energies, structures, and properties in liquid solution has been deeply revised, in order to extend its range of applications and to improve its accuracy. The main changes effect the definition of solute cavities, of solvation charges and of the PCM operator added to the molecular Hamiltonian, as well as the calculation of energy gradients, to be used in geometry optimizations. The procedure can be equally applied to quantum mechanical and to classical calculations; as shown also with a number of numerical tests, this PCM formulation is very efficient and reliable. It can also be applied to very large solutes, since all the bottlenecks have been eliminated to obtain a procedure whose time and memory requirements scale linearly with solute size. The present procedure can be used to compute solvent effects at a number of different levels of theory on almost all the chemical systems which can be studied in vacuo. © 2002 American Institute of Physics.