X-ray lasers offer new possibilities for creating and probing extreme states of matter. We used intense and short X-ray pulses from the FLASH soft X-ray laser to trigger the explosions of CH4 and CD4 molecules and their clusters. The results show that the explosion dynamics depends on cluster size, and indicate a transition from Coulomb explosion to hydrodynamic expansion in larger clusters. The explosion of CH4 and CD4 clusters shows a strong isotope effect: the heavier deuterons acquire higher kinetic energies than the lighter protons. This may be due to an extended inertial confinement of deuterons vs. protons near a rapidly charging cluster core during exposure. [5,6] and solid samples [7][8][9]. In this paper we follow the X-ray-induced explosion of methane (CH 4 ) and heavy methane (CD 4 ) clusters and compare the results to the explosion of the individual molecules. Clusters are eminently suitable to study size-dependent phenomena in the explosion dynamics, and we employed clusters, containing 1000 to 250000 molecules and corresponding to sizes of 4 -32 nm diameter. Molecular clusters bridge the gap between isolated molecules and bulk condensed material. An understanding of ultrafast explosion dynamics in clusters of various dimensions has relevance to imaging by "diffraction before destruction" [10], plasma physics, and fusion research [11,12].The target response to an intense X-ray pulse depends on the wavelength, the intensity of the field, and the size of the sample. Photoionization liberates electrons, which can escape from small samples, and these positively charged objects undergo a Coulomb explosion. The probability of electrons escaping from a cluster depends on its size [13][14][15]. In larger objects, photoelectrons elicit secondary electron cascades and these create additional ionizations. As the overall positive charge of the sample increases during the pulse, photoelectrons will not be able to escape the growing positive potential [13,16]. Trapped photoelectrons create more cascades and the electrons move inwards to neutralize the core of the cluster, leaving behind a positively charged outer layer, which then peels off [17][18][19][20][21]. As a result, large samples burn from the outside inwards. The core of such large objects expands hydrodynamically due to the growing electron pressure within [17,18]. Theoretical studies predict a * Electronic address: nicusor@xray.bmc.uu.se transition from Coulomb explosion to hydrodynamic expansion with increasing sample size [13].The study of Coulomb explosion of molecular clusters with intense infrared lasers has shown the advantage of using heteronuclear molecules, such as CH 4 or CD 4 , to analyze the dynamics of the explosion [22,23]. In a heteronuclear cluster, the light ions can gain additional energy during the explosion by interacting with multiply charged heavy ions (C n+ ). This kinematic effect would be indicative of a Coulomb process, while in a hydrodynamics expansion all the cluster constituents are expected to gain the same energy. We ...