MCSCF Study of Chemical Reactions in Solution within the

Polarizable Continuum Model and VB Analysis of the

Reaction Mechanism
Claudio Amovilli, Franca Maria Floris and Benedetta Mennucci
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35,
56126 Pisa, Italy

1. Introduction

In the theoretical study of chemical processes is difficult to get a full description by

means of a unique methodology. A combination of different techniques and models is
often requested for the detailed comprehension of the problem and for the correct
application of the techniques themselves.
In this work we present a study of the potential energy surfaces (PES) for some
simple chemical processes in aqueous solution, combining the polarizable continuum
model (PCM) with the CASSCF methodology and interpreting the results in a valence
bond (VB) formalism.
The accurate calculation of such surfaces allows the definition of the geometries of
intermolecular complexes, of intermediates and transition states and is useful for further
studies of molecular dynamics, reaction kinetics, vibronic couplings etc. The PCM is
here used to describe the solvent effect, the CASSCF to perform the calculation in a
multiconfigurational framework and the VB to analyze the process from a chemical
point of view.
The main interest of the present study is to illustrate a simple strategy to understand
the complexity of a PES which, very frequently, shows different possible reaction
channels even for the electronic ground state. In many cases it is helpful to find the
most important many-electron configurations, namely the structures in a VB formalism,
with which to describe the main variations in the wavefunction when the geometry
changes. The energy surface for each individual term becomes much simpler and,
combined with the weight that each term has in the wavefunction, gives an explanatory
model for the description of the processes under investigation.
The VB analysis of CASSCF wavefunctions is nowadays a matter of study in many
research groups (see for example [1–5]) thanks to the large diffusion of the CASSCF
computer codes and to the clearcut significance of the VB structures in terms of which
a CASSCF wavefunction can be expanded.
By way of examples we have considered the following three processes in aqueous
solution:

i) the dissociation of sodium chloride;

ii) the Menshutkin reaction between methyl-chloride and ammonia;
iii) the electrophilic attachment of chlorine to ethylene.
The above reactions show ionic products and thus, owing to the energy required for the
separation of charges of opposite sign, do not take place in the gas phase. For these
A. Hernández-Laguna et al, (eds.), Quantum Systems in Chemistry and Physics, Vol. 2: Advanced Problems
and Complex Systems, 213–231.
© 2000 Kluwer Academic Publishers. Printed in Great Britain.