The liquid -> vapor transition of a series of n-alkanes is explored by means of molecular dynamics simulations. From the comparison of the vaporization of methane, pentane and decane we elaborate the dependence of the nucleation mechanisms on the chain length. While the boiling of methane may be characterized as 'ideal' vapor bubble nucleation and growth, our studies related to pentane and decane reveal an increasing importance of liquid droplets acting as intermediates of the vaporization process. With increasing chain length the investigated n-alkanes were found to avoid the formation of large liquid-vapor interfaces by following a different nucleation mechanism. (C) 2008 Elsevier B. V. All rights reserved.