Development of a “First Principles” Water Potential with Flexible Monomers. II: Trimer Potential Energy Surface, Third Virial Coefficient, and Small Clusters

Babin, Volodymyr; Medders, Gregory R.; Paesani, Francesco

doi:10.1021/ct500079y

Cited by 421 publications

(715 citation statements)

References 51 publications

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“…80 Although highly accurate ab initio water potentials have recently become available (e.g., see Refs. [81][82][83][84][85][86][87][88], their integration in MD simulations of MOFs is still prohibitive due to the existing incompatibility with the force fields currently used to describe the frameworks.…”

Section: Computational Methodologymentioning

confidence: 99%

Water Structure and Dynamics in Homochiral [Zn(l-L)(X)] Metal–Organic Frameworks

2015

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The structural, thermodynamic, and dynamical properties of water adsorbed in two homochiral metal-organic frameworks (MOFs) with general formula [Zn(l-L)(X)], X = Cl and Br, and L = 3-methyl-2-(pyridin-4-ylmethylamino)-butanoic acid, are investigated through molecular dynamics simulations. Water molecules establish distinct hydrogen-bonding patterns within the pores of the two MOFs, which directly correlate with the strength of the underlying framework-water interactions. In particular, at low loading, the Zn-Cl groups of [Zn(l-L)(Cl)] effectively provide a templating scaffold for the formation of one-dimensional hydrogen-bonded water chains that propagate along the MOF channels following the helicity of the framework. In contrast, the relatively weaker framework-water interactions in [Zn(l-L)(Br)] lead to less ordered water distributions inside the pores. The simulation results are in agreement with the available experimental data and provide molecular-level insights into specific hydrogen-bonding motifs and spatial arrangements of the water molecules inside the pores, which can be related to the different proton conductivities measured for the two MOFs.

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Section: Computational Methodologymentioning

confidence: 99%

Water Structure and Dynamics in Homochiral [Zn(l-L)(X)] Metal–Organic Frameworks

2015

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“…The cluster dynamics can be probed by high-resolution rovibrational spectroscopy (1)(2)(3)(4)(5)(6)(7)(8)(9) and interpreted by theoretical simulations (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27). The nature of the interactions between the water molecules is the same in the clusters as in the bulk (many-body forces beyond the three-body term are relatively weak) (28), and hence the cluster spectra can be used to test universal models (25,(29)(30)(31)(32) of the water intermolecular potential energy surface, giving insight into hydrogen bonding in all phases of water. At low temperatures, the molecules are frozen into a network and can only rearrange by quantum tunneling, which causes splittings in the spectrum ranging from MHz to THz (33).…”

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confidence: 99%

Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism

Richardson

Pérez

Lobsiger

et al. 2016

Science

306

323

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Citation for published item:ihrdsonD teremy yF nd ¡ erezD grist¡ ol nd vosigerD imon nd eidD edm eF nd emelsoD ferhne nd hieldsD qeorge gF nd uisielD igniew nd lesD hvid tF nd teD frooks rF nd elthorpeD turt gF @PHITA 9gonerted hydrogenEond reking y quntum tunneling in the wter hexmer prismF9D ieneFD QSI @TPUWAF ppF IQIHEIQIQF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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“…32,33 The final model considered here is the many-body MBpol PES and the associated MB-µ DMS, recently developed by us. 15 Both MB-pol PES [34][35][36] and MB-µ DMS 15 were independently developed by using the many-body expansion of the interaction energy (and its derivatives with respect to electric fields),…”

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On the interplay of the potential energy and dipole moment surfaces in controlling the infrared activity of liquid water

Medders

Paesani

2015

The Journal of Chemical Physics

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Infrared vibrational spectroscopy is a valuable tool for probing molecular structure and dynamics. However, obtaining an unambiguous molecular-level interpretation of the spectral features is made difficult, in part, due to the complex interplay of the dipole moment with the underlying vibrational structure. Here, we disentangle the contributions of the potential energy surface (PES) and dipole moment surface (DMS) to the infrared spectrum of liquid water by examining three classes of models, ranging in complexity from simple point charge models to accurate representations of the many-body interactions. By decoupling the PES from the DMS in the calculation of the infrared spectra, we demonstrate that the PES, by directly modulating the vibrational structure, primarily controls the width and position of the spectroscopic features. Due to the dependence of the molecular dipole moment on the hydration environment, many-body electrostatic effects result in a ∼100 cm(-1) redshift in the peak of the OH stretch band. Interestingly, while an accurate description of many-body collective motion is required to generate the correct (vibrational) structure of the liquid, the infrared intensity in the OH stretching region appears to be a measure of the local structure due to the dominance of the one-body and short-ranged two-body contributions to the total dipole moment.

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Development of a “First Principles” Water Potential with Flexible Monomers. II: Trimer Potential Energy Surface, Third Virial Coefficient, and Small Clusters

Cited by 421 publications

References 51 publications

Water Structure and Dynamics in Homochiral [Zn(l-L)(X)] Metal–Organic Frameworks

Water Structure and Dynamics in Homochiral [Zn(l-L)(X)] Metal–Organic Frameworks

Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism

On the interplay of the potential energy and dipole moment surfaces in controlling the infrared activity of liquid water

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