In this paper, we present a new computational QM method for the study of structural properties (i.e. equilibrium geometry) of molec- ular systems at very high pressure. The procedure is based on the polarizable continuum model (PCM) method, usually used to study molecular solutes under standard pressure conditions. The paper considers two critical items: the definition of the pressure and the elab- oration of an analytical code for the calculation of molecular gradients. The method has been developed at HF and DFT levels, with computational costs comparable with those of similar calculations in vacuo. The numerical examples regarding the equilibrium geome- tries and conformational energies of 1,3-butadiene under high pressure give an indication of the potentialities of the approach and of the problems to which it may be applied.
Towards the elaboration of a QM method to describe molecular solutes under the effect of a very high pressure
MENNUCCI, BENEDETTA;
2008
Abstract
In this paper, we present a new computational QM method for the study of structural properties (i.e. equilibrium geometry) of molec- ular systems at very high pressure. The procedure is based on the polarizable continuum model (PCM) method, usually used to study molecular solutes under standard pressure conditions. The paper considers two critical items: the definition of the pressure and the elab- oration of an analytical code for the calculation of molecular gradients. The method has been developed at HF and DFT levels, with computational costs comparable with those of similar calculations in vacuo. The numerical examples regarding the equilibrium geome- tries and conformational energies of 1,3-butadiene under high pressure give an indication of the potentialities of the approach and of the problems to which it may be applied.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
