We present a new implementation of the polarizable continuum model (PCM) at the multiconfigurational self-consistent field (MCSCF) level. This new MCSCF-PCM implementation is based on a second-order algorithm for the optimization of the wave function of the solvated molecule. The robust convergence properties of this approach allows for fast convergence of the PCM-MCSCF wave function for large MCSCF expansions as well as for excited states of solvated molecules. Our implementation also enables us to treat nonequilibrium solvation-that is, to treat excited molecular states generated in a fast excitation process such that not all degrees of freedom of the solvent have relaxed. To demonstrate the applicability of the approach we present calculations of solvation effects on 1,3-dipolar systems and on the ground and excited states of methylenecyclopropene
A second-order, quadratically convergent multiconfigurational self-consistent field polarizable continuum model for equilibrium and nonequilibrium solvation / Cammi, Roberto; R, Frediani; L, Mennucci; B, Tomasi; J, Ruud; K, Mikkelsen. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 117:(2002), pp. 13-13. [10.1063/1.1480871]
A second-order, quadratically convergent multiconfigurational self-consistent field polarizable continuum model for equilibrium and nonequilibrium solvation
CAMMI, Roberto
;
2002-01-01
Abstract
We present a new implementation of the polarizable continuum model (PCM) at the multiconfigurational self-consistent field (MCSCF) level. This new MCSCF-PCM implementation is based on a second-order algorithm for the optimization of the wave function of the solvated molecule. The robust convergence properties of this approach allows for fast convergence of the PCM-MCSCF wave function for large MCSCF expansions as well as for excited states of solvated molecules. Our implementation also enables us to treat nonequilibrium solvation-that is, to treat excited molecular states generated in a fast excitation process such that not all degrees of freedom of the solvent have relaxed. To demonstrate the applicability of the approach we present calculations of solvation effects on 1,3-dipolar systems and on the ground and excited states of methylenecyclopropeneI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
