Infrared Spectrum of the Protonated Water Dimer in the Gas Phase

Fridgen, Travis D.; McMahon, T. B.; MacAleese, Luke; Lemaire, Joël; Maître, Philippe

doi:10.1021/jp040486w

Cited by 175 publications

(237 citation statements)

References 22 publications

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“…The fit for the protonated dimer (Zundel) has an rOO of 2.42 Å, and the excess proton is approximately equidistant from the two oxygens (Fig. 3b), in agreement with experimental [41,49] and theoretical findings [50]. The deprotonated dimer (Fig.…”

Section: Monomers: Water Hydronium and Hydroxidesupporting

confidence: 81%

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

et al. 2011

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Proton transfer to and from water is critical to the function of water in many settings. However, it has been challenging to model. Here, we present proof-of-principle for an efficient yet robust model based on Lewis-inspired submolecular particles with interactions that deviate from Coulombic at short distances to take quantum effects into account. This "LEWIS" model provides excellent correspondence with experimental structures for water molecules and water clusters in their neutral, protonated and deprotonated forms, reasonable values for the proton affinities of water and hydroxide, a good value for the strength of the hydrogen bond in the water dimer, the correct order of magnitude for the stretch and bend force constants of water, and the expected time course for Grotthuss transport in water chains.

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Section: Monomers: Water Hydronium and Hydroxidesupporting

confidence: 81%

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

et al. 2011

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“…In this study, we carry out SCC-DFTB calculations for the IR spectra of various protonated water clusters in the gas phase and compare the results to experimental spectra, which only became available very recently. [30][31][32][33][34][35][36][37] The experimental spectra exhibit different signatures for protonated water clusters of different sizes as well as for their neutral counterparts. Therefore, these characteristic signatures can be used to probe the possible existence and structure of a ͑protonated/ neutral͒ water network in the active site of enzymes.…”

Section: ͑4͒mentioning

confidence: 99%

The vibrational spectra of protonated water clusters: A benchmark for self-consistent-charge density-functional tight binding

Cui

2007

The Journal of Chemical Physics

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The vibrational spectra of protonated water clusters: A benchmark for selfconsistent-charge density-functional tight binding AbstractProton transfers are involved in many chemical processes in solution and in biological systems. Although water molecules have been known to transiently facilitate proton transfers, the possibility that water molecules may serve as the "storage site" for proton in biological systems has only been raised in recent years. To characterize the structural and possibly the dynamic nature of these protonated water clusters, it is important to use effective computational techniques to properly interpret experimental spectroscopic measurements of condensed phase systems. Bearing this goal in mind, we systematically benchmark the self-consistent-charge density-functional tight-binding �SCC-DFTB� method for the description of vibrational spectra of protonated water clusters in the gas phase, which became available only recently with infrared multiphoton photodissociation and infrared predissociation spectroscopic experiments. It is found that SCC-DFTB qualitatively reproduces the important features in the vibrational spectra of protonated water clusters, especially concerning the characteristic signatures of clusters of various sizes. In agreement with recent ab initio molecular dynamics studies, it is found that dynamical effects play an important role in determining the vibrational properties of these water clusters. Considering computational efficiency, these benchmark calculations suggest that the SCC-DFTB/molecular mechanical approach can be an effective tool for probing the structural and dynamic features of protonated water molecules in biomolecular systems. The vibrational spectra of protonated water clusters: A benchmark for self-consistent-charge density-functional tight binding Proton transfers are involved in many chemical processes in solution and in biological systems. Although water molecules have been known to transiently facilitate proton transfers, the possibility that water molecules may serve as the "storage site" for proton in biological systems has only been raised in recent years. To characterize the structural and possibly the dynamic nature of these protonated water clusters, it is important to use effective computational techniques to properly interpret experimental spectroscopic measurements of condensed phase systems. Bearing this goal in mind, we systematically benchmark the self-consistent-charge density-functional tight-binding ͑SCC-DFTB͒ method for the description of vibrational spectra of protonated water clusters in the gas phase, which became available only recently with infrared multiphoton photodissociation and infrared predissociation spectroscopic experiments. It is found that SCC-DFTB qualitatively reproduces the important features in the vibrational spectra of protonated water clusters, especially concerning the characteristic signatures of clusters of various sizes. In agreement with recent ab initio molecular dynamics studies, it is found that dynamic...

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“…The infrared spectroscopy of this cation has been studied extensively in the past both theoretically 59-64 and experimentally, [65][66][67][68][69] and it contains features that one should not even hope to capture using a method that neglects real time quantum interference effects. Among other things, the low temperature spectrum in the shared proton region contains a doublet feature that has been interpreted as a Fermi resonance involving a fourth-order coupling between the proton transfer mode, the O-O stretching mode, and the H-O-H wagging mode.…”

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confidence: 99%

How to remove the spurious resonances from ring polymer molecular dynamics

Rossi

Ceriotti

Manolopoulos

2014

The Journal of Chemical Physics

245

347

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Two of the most successful methods that are presently available for simulating the quantum dynamics of condensed phase systems are centroid molecular dynamics (CMD) and ring polymer molecular dynamics (RPMD). Despite their conceptual differences, practical implementations of these methods differ in just two respects: the choice of the Parrinello-Rahman mass matrix and whether or not a thermostat is applied to the internal modes of the ring polymer during the dynamics. Here we explore a method which is halfway between the two approximations: we keep the path integral bead masses equal to the physical particle masses but attach a Langevin thermostat to the internal modes of the ring polymer during the dynamics. We justify this by showing analytically that the inclusion of an internal mode thermostat does not affect any of the desirable features of RPMD: thermostatted RPMD (TRPMD) is equally valid with respect to everything that has actually been proven about the method as RPMD itself. In particular, because of the choice of bead masses, the resulting method is still optimum in the short-time limit, and the transition state approximation to its reaction rate theory remains closely related to the semiclassical instanton approximation in the deep quantum tunneling regime. In effect, there is a continuous family of methods with these properties, parameterised by the strength of the Langevin friction. Here we explore numerically how the approximation to quantum dynamics depends on this friction, with a particular emphasis on vibrational spectroscopy. We find that a broad range of frictions approaching optimal damping give similar results, and that these results are immune to both the resonance problem of RPMD and the curvature problem of CMD.

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Infrared Spectrum of the Protonated Water Dimer in the Gas Phase

Cited by 175 publications

References 22 publications

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

The vibrational spectra of protonated water clusters: A benchmark for self-consistent-charge density-functional tight binding

How to remove the spurious resonances from ring polymer molecular dynamics

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