Liquid methanol Monte Carlo simulations with a refined potential which includes polarizability, nonadditivity, and intramolecular relaxation

Valdéz-González, Maximiliano; Saint-Martı́n, Humberto; Hernández-Cobos, Jorge; Ayala, Regla; Marcos, Enrique Sánchez; Ortega‐Blake, Iván

doi:10.1063/1.2801538

Cited by 25 publications

(10 citation statements)

References 70 publications

(73 reference statements)

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“…This seems to be the best possible model with a single polarizable site and further improvement can only be achieved by introducing mobile charge densities attached to the hydrogens. 103 Then, the parametrization of the water-ion interactions was done and simulations of infinitely diluted aqueous solutions were performed. The resulting structural and dynamical features were compared to the available experimental data and the previously performed theoretical studies.…”

Section: Discussionmentioning

confidence: 99%

Dynamics and Structure of Ln(III)−Aqua Ions: A Comparative Molecular Dynamics Study Using ab Initio Based Flexible and Polarizable Model Potentials

2009

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Aqueous solutions of a light (Nd3+), a middle (Gd3+), and a heavy (Yb3+) lanthanide ion were studied using ab initio based flexible and polarizable analytical potentials in classical molecular dynamics simulations to describe their thermodynamic, structural, and dynamic features. To avoid the spurious demise of O-H bonds, it was necessary to reparametrize an existing water model, which resulted in an improved description of pure water. The good agreement of the results from the simulations with the experimental hydration enthalpies, the Ln(III)-water radial distribution functions, and the water-exchange rates validated the potentials, though the r(Ln-Ow) distances were 6% longer than the experimentally determined values. A nona-coordinated state was found for Nd3+ in 95% of the simulation, with a tricapped trigonal prism (TCTP) geometry; the corresponding water-exchange mechanism was found to be of dissociative interchange (Id) character through a short-lived octa-coordinated transition state in a square antiprism (SQA) geometry. An octa-coordinated state in SQA geometry was found for Yb3+ in 99% of the simulation, and the observed exchange events exhibited characteristics of an interchange (I) mechanism. For Gd3+ an equilibrium was observed between 8-fold SQA and 9-fold TCTP coordinated states that was maintained by the frequent exchange of a water molecule from the first hydration shell with the bulk, thus producing significant deviations from the ideal geometries, and a fast exchange rate. Though strong water-water interactions prevented a full alignment of the dipoles to the ion's electric field, the screening was found large enough as to limit its range to 5 A; water molecules further apart from the ion were found to have the same dipole as the molecules in the bulk, and a random orientation. The interplay among the water-ion and the water-water interactions determined the different coordination numbers and the different dynamics of the water exchange in the first hydration shell for each ion.

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Section: Discussionmentioning

confidence: 99%

Dynamics and Structure of Ln(III)−Aqua Ions: A Comparative Molecular Dynamics Study Using ab Initio Based Flexible and Polarizable Model Potentials

2009

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“…The model was used to study the thermodynamic, dynamic, structural, and dielectric properties of liquid methanol and of a methanol-water mixture [287]. MC simulations of liquid methanol have also been reported using a potential including polarizability, nonadditivity, and intramolecular relaxation [288]. The classical Drude oscillator model implemented in CHARMM was used to study water-ethanol mixtures by Noskov et al .…”

Section: Application Of Polarizable Force Fieldsmentioning

confidence: 99%

Molecular modeling and dynamics studies with explicit inclusion of electronic polarizability: theory and applications

2009

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A current emphasis in empirical force fields is on the development of potential functions that explicitly treat electronic polarizability. In the present article, the commonly used methodologies for modelling electronic polarization are presented along with an overview of selected application studies. Models presented include induced point-dipoles, classical Drude oscillators, and fluctuating charge methods. The theoretical background of each method is followed by an introduction to extended Langrangian integrators required for computationally tractable molecular dynamics simulations using polarizable force fields. The remainder of the review focuses on application studies using these methods. Emphasis is placed on water models, for which numerous examples exist, with a more thorough discussion presented on the recently published models associated with the Drudebased CHARMM and the AMOEBA force fields. The utility of polarizable models for the study of ion solvation is then presented followed by an overview of studies of small molecules (e.g. CCl 4 , alkanes, etc) and macromolecule (proteins, nucleic acids and lipid bilayers) application studies. The review is written with the goal of providing a general overview of the current status of the field and to facilitate future application and developments.

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“…[17][18][19][20][21][22][23] Methanol has been the subject of a number of recent theoretical and experimental investigations. [24][25][26][27][28][29][30][31] Hyperpolarizabilities of the methanol were reported by Norman et al 32 through the random phase approximation ͑RPA͒ and restricted active space methods using a carefully tested basis set. 33 The calculations reported include vibrational corrections and dispersion effects and were carried out in both gas and liquid phases.…”

Section: Introductionmentioning

confidence: 99%

Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

Dutra

Castro

Fonseca

et al. 2010

The Journal of Chemical Physics

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Basis set convergence of the coupled-cluster correction, MP2CCSD(T): Best practices for benchmarking noncovalent interactions and the attendant revision of the S22, NBC10, HBC6, and HSG databases J. Chem. Phys. 135, 194102 (2011) The electronic spectrum of the previously unknown HAsO transient molecule J. Chem. Phys. 135, 184308 (2011) Accurate ab initio ro-vibronic spectroscopy of the 2 CCN radical using explicitly correlated methods J. Chem. Phys. 135, 144309 (2011) Ab initio investigation of titanium hydroxide isomers and their cations, TiOH0, + and HTiO0, + J. Chem. Phys. 135, 144111 (2011) Additional information on J. Chem. Phys. In this work we present the results for hyperpolarizabilities of the methanol molecule including vibrational corrections and electron correlation effects at the CCSD level. Comparisons to random phase approximation results previously reported show that the electron correlation is in general important for both electronic contribution and vibrational corrections. The role played by the anharmonicities on the calculations of the vibrational corrections has also been analyzed and the obtained results indicate that the anharmonic terms are important for the dc-Pockels and dc-Kerr effects. For the other nonlinear optical properties studied the double-harmonic approximation is found to be suitable. Comparison to available experimental result in gas phase for the dc-second harmonic generation second hyperpolarizability shows a very good agreement with the electronic contribution calculated here while our total value is 14% larger than the experimental value.

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Liquid methanol Monte Carlo simulations with a refined potential which includes polarizability, nonadditivity, and intramolecular relaxation

Cited by 25 publications

References 70 publications

Dynamics and Structure of Ln(III)−Aqua Ions: A Comparative Molecular Dynamics Study Using ab Initio Based Flexible and Polarizable Model Potentials

Dynamics and Structure of Ln(III)−Aqua Ions: A Comparative Molecular Dynamics Study Using ab Initio Based Flexible and Polarizable Model Potentials

Molecular modeling and dynamics studies with explicit inclusion of electronic polarizability: theory and applications

Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

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