Helical ordering in free clusters of cyclic organic – growth & structure

Ashok Bhowmick

Technical Physics & Prototype Engineering Division, BARC, Trombay, Mumbai, India

Sunil K. Ghosh

Bio Organic Division, BARC, Trombay, Mumbai, India

ashokb@apsara.barc.ernet.in

Clusters of organics and metal-organic sandwiches have recently attracted the attention of
many researchers [1-2]. We have studied the formation of large free clusters of
cyclopentanone in gas phase through electrospray-TOF technique. As characteristic to the
ionization process, all the clusters are detected to be multiply charged. The single charge mass
spectrum is computed by deconvoluting the m/z spectrum using the standard routine [3]
normally applied to the analysis of peptide and protein electrospray spectra. Fig. 1 shows the
TOF spectra for both the m/z and mass domains together. The measurement has been carried
out using the high resolution TOF spectrometer reported earlier [4]. The mass of each cluster
essentially turns out to be the mass of an integral number of monomers with some hydrogen
losses which could be attributed to C-C formation between monomers. The clusters are
probably formed with highly symmetric arrangement of monomers coordinated through the
oxygen atoms and occasional C-C formation giving rise to a helical conformation. The base
structural repetition unit comprise of an association of six monomers. The calculated [5]
minimum energy configuration shows 3D non-planner cyclic arrangement forming a helical
ordering. Fig. 2 shows the probable structures of species H (lowest +1 mass) and C.

H C
Fig. 2

1] S. M. Hurley, T. E. Dermota, D. P. Hydutsky, A. W. Castleman Jr., Int. J. Mass

Spectrometry, 228 (2003) 677
[2] A. Graja, B. R. Bulka, F. Kajzar, Proc. NATO Advanced Research Wksp., (2002),
Kluwer Acaemic Publishers, Dordrecht, Netherlands.
[3] Z. Zhang and A. G. Marshall, J. Am. Soc. Mass Spectrom., 9 (1998) 225
[4] A. Bhowmick, W. C. J. Carvalho, A. V. Korgaonkar, J. V. Yakhmi, V. C. Sahni, Int. J.
Mod. Phys. B, 19 (2005) 2621
[5] CS Chem 3D, Cambridge Soft Corporation, Cambridge, MA 02139 USA