We have investigated different approaches to handling parallel-tempering Monte Carlo (PTMC) simulations in the isothermal-isobaric ensemble of molecular cluster/nanoparticle systems for predicting structural phase diagram transitions. We have implemented various methodologies that consist of treating pressure implicitly through its effect on the volume. Thus, the main problem in the simulations under nonzero pressure becomes the volume definition of the finite nonperiodic system, and we considered approaches based on the particles' coordinates. Various volume models, namely container-volume, particle-volume, average-volume, ellipsoids-volume, and convex hull-volume, were employed, and the required corrections for each of them in the Monte Carlo computations were introduced. Finally, we explored the effects of volume/pressure changes for all models on structural phase transitions of a test system, such as the small "icelike" (H2O)12 water cluster. The temperature and pressure dependence of the cluster's heat capacity and energy-volume Pearson correlation coefficient were studied, phase diagrams were constructed using a multiple-histogram method, and attempts were made to identify phase transitions to particular cluster structures. Our results show significant differences between the employed volume models, and we discuss all pressure-induced, such as solid-solid-, solid-liquid-, and liquid-gas-like, phase transformations in the present study.

Donostia International Physics Center Paseo Manuel de Lardizabal 4 20018 Donostia San Sebastián Gipuzkoa Spain

Institute of Fundamental Physics CSIC Serrano 123 28006 Madrid Spain

IT4Innovations VŠB Technical University of Ostrava 17 Listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

Olga Havlová Grammar School Marie Majerové 1691 708 00 Ostrava Poruba Czech Republic

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