2016 
Loboda, O., Ingrosso, F., RuizLópez, M. F., Reis, H., & Millot, C. (2016). Dipole and quadrupole polarizabilities of the water molecule as a function of geometry: FULL PAPER. Journal of Computational Chemistry, .


Loboda, O., Ingrosso, F., RuizLópez, M. F., Szalewicz, K., & Millot, C. (2016). Geometrydependent distributed polarizability models for the water molecule. The Journal of Chemical Physics, 144(3), 034304.


2014 
Millot, C., Chaumont, A., Engler, E., & Wipff, G. (2014). Distributed Polarizability Models for ImidazoliumBased Ionic Liquids. J. Phys. Chem. A, 118(38), 8842–8851.
Résumé: Quantum chemical calculations are used to derive distributed polarizability models sufficiently accurate and compact to be used in classical molecular dynamics simulations of imidazoliumbased room temperature ionic liquids. Two distributed polarizability models are fitted to reproduce the induction energy of three imidazolium cations (1,3dimethyl, 1ethyl3methyl, and 1butyl3methylimidazolium) and four anions (tetrafluoroborate, hexafluorophosphate, nitrate, and thiocyanate) polarized by a point charge located successively on a grid of surrounding points. The first model includes chargeflow polarizabilities between firstneighbor atoms and isotropic dipolar polarizability on all atoms (except H), while the second model includes anisotropic dipolar polarizabilities on all atoms (except H). For the imidazolium cations, particular attention is given to the transferability of the distributed polarizability sets. The molecular polarizability and its anisotropy rebuilt by the distributed models are found to be in good agreement with the exact ab initio values for the three cations and 23 additional conformers of 1ethyl3methyl, 1butyl3methyl, 1pentyl3methyl, and 1hexyl3methylimidazolium cations.


2012 
Ahmad, N., Adnan, R., Soetens, J.  C., & Millot, C. (2012). Molecular Dynamics simulations of liquid isoquinoline as a function of temperature. Chemical Physics, 407, 29–38.
Résumé: Molecular Dynamics simulations of isoquinoline in liquid phase have been conducted in the temperature range 300–365 K corresponding to the normal liquid phase in order to investigate the evolution of translational and rotational diffusion with temperature. Molecules are supposed to be rigid and interact through an allatom potential composed of Coulombic and LennardJones terms. Translational diffusion coefficients are computed from velocity autocorrelation functions and mean square displacement. Anisotropic rotational diffusion coefficients are computed from angular velocity autocorrelation functions. The evolution of the 13C spin–lattice relaxation time with temperature has been obtained from the simulations and compared with experimental results. A small nonArrhenius behavior, more pronounced than what was observed experimentally, has been found for this property. The structure has been analyzed in terms of populations of different kinds of firstneighbor dimers. A continuous evolution of the structure with temperature has been observed. The general trend is thus a continuous smooth evolution of the structure at dimer level and a slight nonArrhenius evolution for diffusion coefficients and reorientational correlation times. These results are compared with those obtained for liquid quinoline where a clear nonArrhenius break around 290 K was observed for the 13C spin–lattice relaxation time from experiments [D. Jalabert, J.B. Robert, H. RouxBuisson, J.P. Kintzinger, J.M. Lehn, R. Zinzius, D. Canet, P. Tekely, Europhys. Lett. 15 (1991) 435] and from simulations [C. Millot, J.C. Soetens, N. Ahmad, R. Adnan, Europhys. Lett. 96 (2011) 43002]. Moreover, the identification of break temperatures for liquid isoquinoline appears to be less clear than for quinoline.
MotsClés: Anisotropic rotational diffusion; Isoquinoline; Liquid state; Molecular Dynamics simulation; Translational diffusion


Soetens, J.  C., Ahmad, N., Adnan, R., & Millot, C. (2012). Molecular Dynamics Simulations of Quinoline in the Liquid Phase. J. Phys. Chem. B, 116(19), 5719–5728.
Résumé: Molecular dynamics simulations of liquid quinoline have been performed at experimental densities corresponding to the temperature range 276?320 K. The intermolecular potential is a simple effective twobody potential between rigid molecules having 17 atomic LennardJones and electrostatic Coulomb interaction sites. The vaporization enthalpy is overestimated by 8?9% with respect to the experimental value. The translational diffusion coefficient exhibits a small nonArrhenius behavior with a change in temperatures near 290 and 303 K. The rotational diffusion tensor is rotated around the z axis perpendicular to the molecular plane by an angle of 4?6° with respect to the frame of reference defined by the principal axes of inertia. The rotational diffusion tensor presents a significant anisotropy with Drot,y/Drot,x ? 0.6?0.5 and Drot,z/Drot,x ? 1.6?1.3 between 276 and 320 K when the x axis is defined as the long molecular axis and the y axis is situated nearly along the central C?C bond. The rotational diffusion coefficients, the reorientational correlation times of the C?H vectors, and the T113C NMR relaxation times present a nonArrhenius break around 288?290 K in agreement with several experimental results. In addition, a nonArrhenius break can also be observed at 303 K for these properties. It has been found that the structure evolves smoothly in the studied temperature range. Center of mass?center of mass and atom?atom radial distribution functions show a monotonous evolution with temperature. Various types of firstneighbor dimers have been defined, and their population analysis has revealed a continuous monotonous evolution with temperature. Thus, the nonArrhenius behavior observed for translational and rotational diffusion is correlated with the monotonous evolution of the population of firstneighbor dimers at a microscopic level and not with a sharp structural transition.


2011 
Millot, C., Soetens, J.  C., Ahmad, N., & Adnan, R. (2011). Molecular simulation of unusual dynamical properties of quinoline in liquid phase. Epl, 96(4), 43002.
Résumé: Moleculardynamics simulations of liquid quinoline between 276 and 320 K and liquid isoquinoline between 300 and 365 K have been done using a simple effective atomatom potential. The translational diffusion coefficient of quinoline is found to present a small nonArrhenius behavior. Rotational diffusion coefficients, secondorder reorientational correlation times of the CH vectors and T 1 13 C NMR relaxation times of quinoline reproduce the nonArrhenius break around 290 K observed experimentally for quinoline by different experimental techniques. Isoquinoline seems to present a nonArrhenius behavior, too, though with less clear break temperatures. Such behaviors are correlated with a smooth continuous evolution of the structure at dimer level.


2010 
Millot, C., Schurhammer, R., Engler, E., & Wipff, G. (2010). Simulation and UVvisible spectra of organic dyes in subcritical and supercritical carbon dioxide. Journal of Molecular Liquids, 153(1), 37–45.
Résumé: Ab initio calculations have been used to adapt the AMBER force field to three organic dyes (CI disperse red 82, CI disperse blue 60 and CI disperse yellow 211) that are interesting for industrial textile dying processes in supercritical carbon dioxide. For each dye molecule in carbon dioxide solution, Molecular Dynamics simulations with periodic boundary conditions have been performed for three thermodynamic conditions (278 K, 50 atm; 278 K, 400 atm; 373 K, 400 atm) to obtain structural, thermodynamical and dynamical properties. From the red dye/CO2 and the blue dye/CO2 trajectories, one hundred of uncorrelated configurations have been extracted to compute the UV/vis absorption spectra with the INDO/CIS method. Quantitative agreement with the experimental trend has been observed for the lowest absorption band spectral shift between 278 K, 50 atm and supercritical conditions at 373 K, 400 atm for the red dye/CO2 system.
MotsClés: Carbon dioxide; CI disperse blue 60; CI disperse red 82; CI disperse yellow 211; Dye; INDO/CIS; Molecular Dynamics simulation

