Directory: Faculty

Valeria Molinero

Valeria Molinero


Associate Professor
Director, Henry Eyring Center for Theoretical Chemistry

Ph.D. University of Buenos Aires, 1999
Postdoctoral Researcher, California Institute of Technology, 2000-2003
Associate Researcher, Arizona State University, 2005-2006
Associate Scientist, California Institute of Technology, 2003-2006

Phone: (801) 585-9618

Office: 4623 Thatcher Building


Research Group


Activities & Awards

  • Camille Dreyfus Teacher-Scholar Award, 2012
  • College of Science Myriad Faculty Award for Research Excellence, 2011
  • Beckman Young Investigator Award, 2009
  • Helmholtz Award, International Association for the Properties of Water and Steam, 2005

Research Interests

We use computer simulations, statistical mechanics and develop novel models to investigate the interplay between microscopic structure, dynamics and phase transformations in disordered materials.

Structure and anomalies of liquid water and its solutions. Liquid water presents a series of thermodynamic, structural and dynamical anomalies that become the most pronounced in the supercooled region of the phase diagram. We investigate the origin of the anomalies, the development of long-range structural correlations in supercooled liquid water and the effect of the increase in the tetrahedrality of liquid water on the structure and phase segregation of aqueous solutions of salts.

decoupled diffusion of ions

Nanophase segregation of aqueous solutions of LiCl as they are vitrified through hyperquenching.

Mechanisms of ice crystallization in bulk and confined water. One of water’s unsolved puzzles is what determines the lowest temperature at which liquid water and aqueous solutions can be cooled before freezing to ice. We use molecular simulations to elucidate the mechanism of water freezing and its relation to the thermodynamics and structure of supercooled water.

decoupled diffusion of ions

Development of cubic (red) and hexagonal (green) ice in the crystallization of liquid water at 180 K.

Nanoconfinement affects the phase behavior of water. Our work demonstrates that a bilayer of water can form a variety of novel structures based on pentagons, including a dodecagonal quasicrystal.

Nucleation and Growth of Clathrate Hydrates. Clathrate hydrates are crystalline inclusion compounds of water and small molecules that such as carbon dioxide or methane. The concentration of the gas molecules in the hydrates is about 100 times larger than in solution. A main question is how do the clathrates form if the water and gas do not mix. We use molecular dynamics simulations with efficient coarse-grained models to investigate the stability and mechanisms of nucleation and growth of clathrate hydrates of guests with a wide range of sizes and hydrophilicity. The main questions we address are what are the structures of the clathrate nuclei and what are the mechanisms of their formation from two-phase fluid systems and from ice.

decoupled diffusion of ions

Our simulations unravel a multistep mechanism of nucleation of clathrate hydrates that involves amorohous intermediates. Our work demonstrates that amorphous nuclei can grow crystalline clathrates.

The state of water in nanoporous and nanostructured materials. Water is ubiquitous in biological and synthetic materials, where is often confined by a matrix. A goal of our research is to understand how the structure of the material and intermolecular interactions determine the distribution of water and the stability and metastability of water’s liquid state. We investigate disordered systems with soft confinement, where the matrix is a rubbery polymer or a viscous supercooled liquid, and with hard confinement, such as mesoporous silica.

Hydrated Nafion in a multi-scale heterogenous material
nanostructure of hydrated Nafion
Coarse Grained Modeling Atomistic & Coarse Grained Modeling Atomistic Simulations
decoupled diffusion of ions

Development of coarse-grained models.Most of our work involves the study of phenomena that occur over times that makes them inaccessible to state of the art atomistic simulations. To address this issue we have developed very efficient coarse-grained molecular models of water, electrolytes, solvated DNA, and methane. For example, water can be modeled as an element of the group IV with tetrahedrality intermediate between carbon and silicon. The goal of developing coarse-grained models is two-fold: First, to simulate much longer time scales and larger systems at a small fraction of the computing cost, and thus to build the tools needed to tackle new, and so far untreatable, problems. The second, and most fundamental, goal of developing coarse-grained models is to understand what level of details is needed to reproduce (some? which ones?) physical properties of a substance. In this sense, the coarse-grained model, as all models and theories, allows us to extract a fundamental understanding of the molecular and macroscopic behavior of matter and put our hypothesis (and prejudices!) to test.

topSelected Publications

  • “Thermodynamic and structural signatures of water-driven methane-methane attraction in coarse-grained mW water”, B. Song and V. Molinero, J. Chem. Phys., 139 (2013), 054511.
  • Low-density liquid water is the mother of ice: on the relation between mesostructure, thermodynamics and ice crystallization in solutions”, G. Bullock and V. Molinero, Faraday Discussions, DOI:10.1039/C3FD00085K [invited; cover article].
  • “Stability and metastability of bromine clathrate polymorphs”, A. H. Nguyen and V. Molinero, J. Phys. Chem. B, 117 (2013), 6330-6338.
  • “Nature of the anomalies in the supercooled liquid state of the mW model of water”, V. Holten, D. T. Limmer, V. Molinero and M. A. Anisimov, J. Chem. Phys., 138 (2013), 174501.
  • “Structure, dynamics and phase behavior of water in TiO2 nanopores”, E. Gonzalez Solveyra, E. de la Llave, V. Molinero, G. Soler-Illia, D. A. Scherlis, J. Phys. Chem. C, 117 (2013), 3330–3342.
  • “Homogeneous nucleation of methane hydrates: unrealistic at realistic conditions”, B. C. Knott, V. Molinero, M. F. Doherty and B. Peters, J. Am. Chem. Soc., 134 (2012), 19544–19547.
  • “Structure of the clathrate/solution interface and mechanisms of cross-nucleation of clathrate hydrates”, A. H. Nguyen, L. C. Jacobson and V. Molinero, J. Phys. Chem. C, 116 (2012), 19828–19838.
  • “The quasi-liquid layer of ice under conditions of methane clathrate formation”, T. D. Shepherd, M. A. Koc and V. Molinero, J. Phys. Chem. C, 116 (2012), 12172–12180.
  • “Water-Driven Cavity-Ligand Binding: Comparison of Thermodynamic Signatures from Coarse-Grained and Atomic-Level Simulations”, and V. Molinero, J. Chem. Theory and Comp. 8 (2012), 3696–3704 [invited].
  • “Liquid-ice coexistence below theR. Baron melting temperature for water confined in hydrophilic and hydrophobic nanopores”, E. B. Moore, J. T. Allen and V. Molinero, J. Chem. Phys. C., 116 (2012), 7507-7514.
  • “Crystallization, Melting and Structure of Water Nanodroplets at Atmospherically Relevant Temperatures”, J. C. Johnston and V. Molinero, J. Am. Chem. Soc. 134 (2012), 6650-6659.
  • “Water and Other Tetrahedral Liquids: Order, Anomalies and Solvation B. S. Jabes, D. Nayar, D. Dhabal, V. Molinero and C. Chakravarty, J. Phys. Cond. Matt., 24 (2012) 284116.
  • “Role of Confinement and Surface Affinity on Filling Mechanisms and Sorption Hysteresis in Nanopores”, E. de la Llave, V. Molinero and D. A. Scherlis, J. Phys. Chem. C., 116 (2012) 1833–1840
  • “Structural Transformation in Supercooled Water Controls the Crystallization Rate of Ice”, E. B. Moore and V. Molinero*, Nature, 479 (2011), 506-508.
  • “Is it cubic? Ice crystallization from deeply supercooled water”, E. B. Moore and V. Molinero*, Phys. Chem. Chem. Phys. 13 (2011), 20008-20016.
  • “Is there a liquid-liquid transition in confined water?”, L. Xu* and V. Molinero*, J. Phys. Chem. B 115 (2011), 14210–14216 [invited].
  • “Melting and crystallization of ice in partially filled nanopores”, E. Gonzalez Solveyra, E. de la Llave, D. A. Scherlis and V. Molinero*, J. Phys. Chem. B. 115 (2011), 14196–14204 [invited].
  • “The Rise and Fall of Anomalies in Tetrahedral Liquids”, W. Hujo, B. S. Jabes, V. K. Rana, C. Chakravarty* and V. Molinero*, J. Stat. Phys. 145 (2011) 293-312.
  • “Order parameters for the multistep crystallization of clathrate hydrates”, L. C. Jacobson, M. Matsumoto and V. Molinero*, J. Chem. Phys. 135 (2011), 074501.
  • “Can Amorphous Nuclei Grow Crystalline Clathrates? The Size and Crystallinity of Critical Clathrate Nuclei”, J. C. Jacobson and V. Molinero*, JACS (2011), 133, 6458-6463.
  • “A Single-Component Silicon Quasicrystal”, Jessica C. Johnston, Spencer Phippen and V. Molinero*, J. Phys. Chem. Lett. (2011), 2, 384-388.
  • “Structural Study of Low Concentration LiCl Aqueous Solutions in the Liquid, Supercooled and Hyperquenched Glassy State”, K. Winkel, M. Seidl, T. Loerting, L. E. Bove, S. Imberti, V. Molinero, F. Bruni, R. Mancinelli and M. A. Ricci*, J. Chem. Phys, (2011), 134, 024515.
  • “Nanophase Segregation in Supercooled Aqueous Solutions and their Glasses Driven by the Polyamorphism of Water”, Ly Le and V. Molinero*, J. Phys. Chem. A. 115 (2011), 5900–5907 [invited].
  • “A Coarse-Grained Model of DNA with Explicit Solvation by Water and Ions”, R. C. DeMille, T.E. Cheatham III and V. Molinero*, J. Phys. Chem. B., 115 (2011), 132-142.
  • “Liquid to quasicrystal transition in bilayer water”, J. C. Johnston, N. Kastelowitz and V. Molinero*, J. Chem. Phys., 133 (2010), 154516.
  • “Nucleation Pathways of Clathrate Hydrates: Effect of Guest Size and Hydrophilicity”, L. C. Jacobson, W. Hujo and V. Molinero*, J. Phys. Chem. B., 114 (2010), 13796–13807.
  • “Amorphous Precursors in the Nucleation of Clathrate Hydrates”, L. C. Jacobson, W. Hujo and V. Molinero*, JACS, 132 (2010), 11806–11811.
  • “Water filling of hydrophilic nanopores”, E. de la Llave, V. Molinero* and D. A. Scherlis*, J. Chem. Phys., 133 (2010), 034513.
  • “Ice crystallization in water’s “no-man’s land””, E. B. Moore and V. Molinero*, J. Chem Phys., 132 (2010), 244504.
  • “A Methane-Water Model for Coarse-Grained Simulations of Solutions and Clathrate Hydrates”, L. Jacobson and V. Molinero*, J. Phys. Chem. B, 114 (2010), 7302-7311.
  • “Liquid-vapor oscillations of water nanoconfined between hydrophobic disks: thermodynamics and kinetics”, L. Xu and V. Molinero*, J. Phys. Chem. B, 114 (2010), 7320-7328.
  • “The Anomalously High Melting Temperature of Bilayer Ice”, N. Kastelowitz, Jessica C. Johnston and V. Molinero*, J. Chem. Phys. 132 (2010), 124511.
  • “Freezing, Melting and Structure of Ice in a Hydrophilic Nanopore”, E.B. Moore, E. de la Llave, K. Welke, D. A. Scherlis and V. Molinero*, Phys. Chem. Chem. Phys. 12 (2010), 4124-4134.
  • “Coarse-grained Ions Without Charges: Reproducing the Solvation Structure of NaCl in water using Short-Ranged Potentials”, R. DeMille and V. Molinero*, J. Chem. Phys. 131, (2009), 034107.
  • “Thermodynamic Stability And Growth Of Guest-Free Clathrate Hydrates, A Low-Density Crystal Phase Of Water”, L. C. Jacobson, W. Hujo and V. Molinero*, J. Phys. Chem. B. (2009), 113, 10298–10307.
  • “Growing correlation length in supercooled water”, E. B. Moore and V. Molinero*, J. Chem. Phys. 130, (2009), 244505. This article was J. Chem. Phys. Editor’s choice 2009.
  • “Water modeled as an intermediate element between carbon and silicon”, V. Molinero*, E. B. Moore, J. Phys. Chem. B, 113 (2009), 4008. [invited]
  • “Vitrification of a monatomic metallic liquid”, M. H, Bhat, V. Molinero, E. Soignard, S. Sastry, J. L Yarger, and C. A. Angell*. Nature, 448 (2007), 787-790.
  • “Tuning of tetrahedrality in a silicon potential yields a series of monatomic (metal-like) glassformers of very high fragility”, V. Molinero, S. Sastry, and C. A. Angell. Phys. Rev. Lett., 97 (2006) 075701.
  • “Multi-paradigm multi-scale simulations for fuel cell catalysts and membranes” W. Goddard III, B. Merinov, A. van Duin, T. Jacib, M. Blanco, V. Molinero, S.S. Jang And Y.H. Jang. Molecular Simulations, 32 (2006) 251–268.
  • “Molecular modeling of carbohydrates with no charges, no hydrogen bonds and no atoms” V. Molinero, and W.A. Goddard III. ACS Symposium Series No. 930, NMR Spectroscopy and Computer Modeling of Carbohydrates, J.F.G. Vliegenthart and R. Woods Ed., ACS, Washington DC, 2006.
  • “Microscopic mechanism of water diffusion in glucose glasses” V. Molinero, and W.A. Goddard III. Phys. Rev. Lett., 95 (2005) 045701.
  • “Fluorinated imidazoles as proton carriers for water-free fuel cell membranes" W. Deng, V. Molinero, and W.A. Goddard III. J. Am. Chem. Soc., 2004, 126, 15644-15645.
  • “The mechanisms of nonexponential relaxations in supercooled glucose solutions: the role of water facilitation" V. Molinero, T. Cagin and W.A. Goddard III. J. Phys. Chem. A 2004, 108, 3699 – 3712.
  • “Nanophase-segregation and transport in Nafion 117 from molecular dynamics simulations: effect of monomeric sequence” S. S. Jang, V. Molinero, T. Cagin, and W.A. Goddard III. J. Phys. Chem. B 2004, 108, 3149-3157.
  • “M3B: a coarse grain force field for the simulation of oligosaccharides and their water mixtures" V. Molinero, and W.A. Goddard III. J. Phys. Chem. B 2004, 108, 1414-1427.
  • “Sugar, water and free-volume networks in concentrated sucrose solutions". V. Molinero, T. Cagin, and W.A. Goddard III. Chem. Phys. Lett. 2003, 377, 469-474.
  • “Dynamics of solvation-induced structural transitions in mesoscopic binary clusters". V. Molinero, D. Laria, and R. Kapral. Phys. Rev. Lett. 2000, 84, 455-458.
  • “Electrostatic interactions at self assembled molecular films of charged thiols on gold”. V. Molinero, and E. J. Calvo. J. Electroanal. Chem. 1998, 17, 17-25.


U.S. patent US60578034, "Fluorinated imidazoles as proton carriers for water-free proton exchange membranes for fuel cells". Inventors: W.A. Goddard III, W. Deng, and V. Molinero.