The spectral line of a dopant molecule B in a cluster B·An of solvent molecules A has usually been thought to converge to the bulk (gas-to-condensate) shift as n → ∞. Size-resolved electronic spectral measurements on a number of systems do appear to show a rapid and then asymptotic convergence, so that nearly all the shift is recovered by n = 30-50. We discuss here a set of examples - B·(N2)n, B·Arn, and Al·Arn (B = benzene) - in which far from bulk shifts are observed even though apparent asymptotes have been reached. Several models are proposed to explain this effect, and their liabilities are discussed.
|Original language||English (US)|
|Number of pages||5|
|Journal||Journal of physical chemistry|
|State||Published - 1991|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry