In this paper we compare the polarization response given by two different chemical potential equalization schemes to be applied to molecular dynamics simulations: the standard fluctuating point charge model (FQ) and the atom-atom charge transfer model (AACT). We have tested the transferability of FQ and AACT parameters, fitted to the polarizability of small size alkanes and polyenes, to large size homologues. We show that the FQ scheme is not adequate for the n-alkanes as it strongly overestimates the polarizability tensor components as the number of carbon atoms increases. The FQ approach has been found more predictive for highly conjugated systems like polyenes, although still unsatisfactory. The AACT parameters tuned on ethane are instead perfectly transferable to alkanes of any length and conformation. The AACT scheme satisfactorily reproduces the polarization response also for highly conjugated systems.

Electrical response in chemical potential equalization schemes / Chelli, Riccardo; Procacci, Piero; Righini, Roberto; Califano, Salvatore. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - STAMPA. - 111:(1999), pp. 8569-8575. [10.1063/1.480198]

Electrical response in chemical potential equalization schemes

CHELLI, RICCARDO;PROCACCI, PIERO;RIGHINI, ROBERTO;CALIFANO, SALVATORE
1999

Abstract

In this paper we compare the polarization response given by two different chemical potential equalization schemes to be applied to molecular dynamics simulations: the standard fluctuating point charge model (FQ) and the atom-atom charge transfer model (AACT). We have tested the transferability of FQ and AACT parameters, fitted to the polarizability of small size alkanes and polyenes, to large size homologues. We show that the FQ scheme is not adequate for the n-alkanes as it strongly overestimates the polarizability tensor components as the number of carbon atoms increases. The FQ approach has been found more predictive for highly conjugated systems like polyenes, although still unsatisfactory. The AACT parameters tuned on ethane are instead perfectly transferable to alkanes of any length and conformation. The AACT scheme satisfactorily reproduces the polarization response also for highly conjugated systems.
1999
111
8569
8575
Chelli, Riccardo; Procacci, Piero; Righini, Roberto; Califano, Salvatore
File in questo prodotto:
File Dimensione Formato  
J.Chem.Phys.-y99_v111_p8569.pdf

Accesso chiuso

Descrizione: Articolo principale
Tipologia: Pdf editoriale (Version of record)
Licenza: Tutti i diritti riservati
Dimensione 85.45 kB
Formato Adobe PDF
85.45 kB Adobe PDF   Richiedi una copia

I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/370491
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 112
  • ???jsp.display-item.citation.isi??? 103
social impact