Collect. Czech. Chem. Commun. 2003, 68, 2292-2296

Linear Scaling with Cluster Size for Calculations of NMR Properties in Liquids

Markus G. Müller and Hanspeter Huber*

Departement Chemie der Universität Basel, Klingelbergstr. 80, CH-4056 Basel, Switzerland


It is shown for liquid water that the contributions of the solvent molecules to the NMR chemical shielding of a proton in the solute molecule is approximately pair-additive. This leads to linear scaling in the computational effort with cluster size if the cluster method is applied. Alternatively, a pair chemical shielding surface, in analogy to the pair potential surface, can be calculated in advance of the simulation. Its analytical fit can be coded into the simulation program to be easily evaluated any time during the simulation, e.g. to get time correlation functions. As water is an extreme case, it is assumed that for other systems an even better additivity might be found.

Keywords: NMR chemical shielding; Pair-additivity; Liquid state; Cluster method; Linear scaling; Molecular dynamics; DQCC.

References: 14 live references.