Calculation of structures and vibrational spectra of acetonitrile clusters

The minimum energy structures of acetonitrile clusters from n = 2 to n = 13 have been calculated using a total cluster potential which is composed fro m a semi-empirical intermolecular potential in combination with the intramo lecular force field. Based on these results the frequency shifts of the CC stretch and the CH3 wag modes are calculated and compared with recent measu rements of size selected free clusters and clusters embedded in large heliu m droplets. The calculations reproduce the coarse structure of the measurem ents and thus demonstrate that the calculated structures with antiparallel molecules as building blocks caused by the multipolar interaction are corre ct. For the trimer and tetramer the spectra obtained in the ultracold heliu m clusters are better reproduced than those of the free clusters indicating that in this experimental arrangement specific isomeric structures are pre sent which are not observed in the warmer free clusters. (C) 1998 Elsevier Science B.V. All rights reserved.