Isolating the Spectral Signatures of Individual Sites in Water Networks Using Vibrational Double-Resonance Spectroscopy of Cluster Isotopomers

Guasco, Timothy L.; Elliott, Ben; Johnson, Mark A.; Ding, Jing; Jordan, Kenneth D.

doi:10.1021/jz100730q

Cited by 32 publications

(29 citation statements)

References 34 publications

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“…Electronic mail: dhlaria@cnea.gov.ar including polar molecules, as well as ions, including excess protons and electrons. [20][21][22][23][24] Since water clusters are normally generated via adiabatic expansions of aqueous vapors that bring their temperature down to the range of ∼100 K or below, one must anticipate that nuclear quantum fluctuations should manifest in a more vivid fashion. 25 Further, since the characteristic vibrational and librational frequencies of water molecules depend on their hydrogen bonding environment, it has long been appreciated that the impact of quantum effects should vary with this environment.…”

Section: Introductionmentioning

confidence: 99%

Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

Videla

Rossky

Laría

2013

The Journal of Chemical Physics

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We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the characteristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H 2 O] 8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydrogen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high frequency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parameterized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynamics, as reported by instantaneous normal modes, are also discussed. © 2013 AIP Publishing LLC.

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Section: Introductionmentioning

confidence: 99%

Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

Videla

Rossky

Laría

2013

The Journal of Chemical Physics

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“…However, some experimental evidence 17 18 19 20 21 22 and theoretical studies 23 have shown the nonadiabatic effects of vibration/electron coupling on flat metal and some metal nanoparticle surfaces 10 24 , questioning the general applicability of the approach. This problem is even more complicated on the surfaces of catalytic metal nanoparticles, as the electronic properties can vary with particle size 25 and surface sites 26 .…”

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confidence: 99%

Two distinctive energy migration pathways of monolayer molecules on metal nanoparticle surfaces

Chen

et al. 2016

Nat Commun

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Energy migrations at metal nanomaterial surfaces are fundamentally important to heterogeneous reactions. Here we report two distinctive energy migration pathways of monolayer adsorbate molecules on differently sized metal nanoparticle surfaces investigated with ultrafast vibrational spectroscopy. On a 5 nm platinum particle, within a few picoseconds the vibrational energy of a carbon monoxide adsorbate rapidly dissipates into the particle through electron/hole pair excitations, generating heat that quickly migrates on surface. In contrast, the lack of vibration-electron coupling on approximately 1 nm particles results in vibrational energy migration among adsorbates that occurs on a twenty times slower timescale. Further investigations reveal that the rapid carbon monoxide energy relaxation is also affected by the adsorption sites and the nature of the metal but to a lesser extent. These findings reflect the dependence of electron/vibration coupling on the metallic nature, size and surface site of nanoparticles and its significance in mediating energy relaxations and migrations on nanoparticle surfaces.

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“…Later, improvements in experimental techniques allowed direct comparison with theoretical results. Photoelectron spectroscopy [18][19][20][21][22][23][24] and vibrational spectroscopy [25][26][27][28][29] techniques have been used to garner information about the structural and electronic properties of water cluster anions. These experiments have provided data for the vertical detachment energy (VDE) of small water clusters.…”

Section: Introductionmentioning

confidence: 99%

Importance of self-interaction-error removal in density functional calculations on water cluster anions

Vargas

Ufondu

Baruah

et al. 2020

Phys. Chem. Chem. Phys.

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Accurate description of the excess charge in water cluster anions is challenging for standard semi-local and (global) hybrid density functional approximations (DFAs). Using the recent unitary invariant implementation of the Perdew-Zunger self-interaction correction (SIC) method using Fermi-Löwdin orbitals, we assess the effect of selfinteraction error on the vertical detachment energies of water clusters anions with the local spin density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation, and the strongly constrained and appropriately normed (SCAN) meta-GGA functionals. Our results show that for the relative energies of isomers with respect to reference CCSD(T) values, the uncorrected SCAN functional has the smallest deviation of 21 meV, better than that for the MP2 method. The performance of SIC-SCAN is comparable to that of MP2 and is better than SIC-LSDA and SIC-PBE, but it reverses the ordering of the two lowest isomers for water hexamer anions. Removing self interaction error (SIE) corrects the tendency of LSDA, PBE, and SCAN to over-bind the extra electron. The vertical detachment energies (VDEs) of water cluster anions, obtained from the total energy differences of corresponding anion and neutral clusters, are significantly improved by removing self-interaction and are better than the hybrid B3LYP functional, but fall short of MP2 accuracy. Removing SIE results in substantial improvement in the position of the eigenvalue of the extra electron. The negative of the highest occupied eigenvalue after SIC provides an excellent approximation to the VDE, especially for SIC-PBE where the mean absolute error with respect to CCSD(T) is only 17 meV, the best among all approximations compared in this work.

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Isolating the Spectral Signatures of Individual Sites in Water Networks Using Vibrational Double-Resonance Spectroscopy of Cluster Isotopomers

Cited by 32 publications

References 34 publications

Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures

Two distinctive energy migration pathways of monolayer molecules on metal nanoparticle surfaces

Importance of self-interaction-error removal in density functional calculations on water cluster anions

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