Van der Waals molecule

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A van der Waals molecule is a stable cluster consisting of two or more molecules held together by van der Waals forces or by hydrogen bonds. The name originated in the beginning of the 1970s when stable molecular clusters were regularly observed in molecular beam microwave spectroscopy. In (supersonic) molecular beams temperatures are very low (usually less than 5 K). At these low temperatures van der Waals (vdW) molecules are stable and can be investigated by microwave and far-infrared spectroscopy. Also in cold equilibrium gases vdW molecules are formed, albeit in small, temperature dependent, concentrations. Rotational and vibrational transitions in vdW molecules have indeed been observed in gases, mainly by UV and IR spectroscopy.

Van der Waals molecules are usually very non-rigid and different versions are separated by low energy barriers, so that tunneling splittings, observable in far-infrared spectra, are relatively large. Thus, in the far-infrared one may observe intermolecular vibrations, rotations, and tunneling motions of vdW molecules (VRT spectroscopy). The VRT spectroscopic study of vdW molecules is one of the most direct routes to the understanding of intermolecular forces.

Examples of well-studied vdW molecules are Ar2, H2-Ar, benzene-Ar, (H2O)2, and (HF)2


  • So far three special issues of Chemical Reviews were devoted to vdW molecules: I. Vol. 88(6) (1988). II. Vol. 94(7) (1994). III. Vol. 100(11) (2000).
  • Early reviews of vdW molecules: G. E. Ewing, Accounts of Chemical Research, Vol. 8, pp. 185-192, (1975): Structure and Properties of van der Waals molecules. B. L. Blaney and G. E. Ewing, Annual Review of Physical Chemistry, Vol. 27, pp. 553-586 (1976): Van der Waals Molecules.
  • About VRT spectroscopy: G. A. Blake, et al., Review Scientific Instruments, Vol. 62, p. 1693, 1701 (1991). H. Linnartz, W.L. Meerts, and M. Havenith, Chemical Physics, Vol. 193, p. 327 (1995).