Infrared Spectroscopy of Water Cluster Anions, (H2O)n=3‐24‐ in the HOH Bending Region: Persistence of the Double H‐Bond Acceptor (AA) Water Molecule in the Excess Electron Binding Site of the Class I Isomers.

Roscioli, Joseph R.; Hammer, Nathan I.; Johnson, Mark A.

doi:10.1002/chin.200635002

Cited by 8 publications

(10 citation statements)

References 1 publication

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“…The fact that water anion clusters indeed have different Hbond stabilization motifs is known from IR photodetachment spectroscopy experiments, which observed a splitting of the water bending vibration consistent with D and AA waters binding the excess electron. 37,45 For small cluster anions with 7−8 waters, the AA binding motif was shown to correspond to the higher-energy peak in the photoelectron spectrum and the D binding motif to the lower-energy peaks, 46 a finding consistent with ab initio calculations performed on a few static anion cluster geometries. 47 Our observation that D and AA binding motifs are preferred for metastable and thermally equilibrated water anion cluster configurations makes sense.…”

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confidence: 69%

Thermal Equilibration Controls H-Bonding and the Vertical Detachment Energy of Water Cluster Anions

Zho

Vlček

Neuhauser

et al. 2018

J. Phys. Chem. Lett.

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One of the outstanding puzzles in the photoelectron spectroscopy of water anion clusters, which serve as precursors to the hydrated electron, is that the excess electron has multiple vertical detachment energies (VDEs), with different groups seeing different distributions of VDEs. We have studied the photoelectron spectroscopy of water cluster anions using simulation techniques designed to mimic the different ways that water cluster anions are produced experimentally. Our simulations take advantage of density functional theory-based Born-Oppenheimer molecular dynamics with an optimally tuned range-separated hybrid functional that is shown to give outstanding accuracy for calculating electron binding energies for this system. We find that our simulations are able to accurately reproduce the experimentally observed VDEs for cluster anions of different sizes, with different VDE distributions observed depending on how the water cluster anions are prepared. For cluster anion sizes up to 20 water molecules, we see that the excess electron always resides on the surface of the cluster and that the different discrete VDEs result from the discrete number of hydrogen bonds made to the electron by water molecules on the surface. Clusters that are less thermally equilibrated have surface waters that tend to make single H-bonds to the electron, resulting in lower VDEs, while clusters that are more thermally equilibrated have surface waters that prefer to make two H-bonds to the electron, resulting in higher VDEs.

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confidence: 69%

Thermal Equilibration Controls H-Bonding and the Vertical Detachment Energy of Water Cluster Anions

Zho

Vlček

Neuhauser

et al. 2018

J. Phys. Chem. Lett.

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“…23,55 Similar downshift of the OH bending modes was previously reported on water clusters having an excess electron. [76][77][78] demonstrated that an extra electron bonded to a water molecule with the two hydrogen not involved in hydrogen bonds, so-called double HB acceptor (AA) configuration, shifts the OH bending mode down to 1540 cm −1 . 76 The strong redshift of the bending mode frequency was explained by a charge transfer of the excess electron to the σ* OH antibonding orbital of the water molecule, stabilizing the extra electron.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Unusual Water Hydrogen Bond Network around Hydrogenated Nanodiamonds

et al. 2017

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Nanodiamonds exhibit exceptional colloidal properties in aqueous media that lead to a wide range of applications in nanomedicine and other fields. Nevertheless, the role of surface chemistry on the hydration of nanodiamonds remains poorly understood. Here, we probed the water hydrogen bond network in aqueous dispersions of nanodiamonds by infrared, Raman, and X-ray absorption spectroscopies applied in situ in aqueous environment. Aqueous dispersions of nanodiamonds with hydrogenated, carboxylated, hydroxylated, and polyfunctional surface terminations were compared. A different hydrogen bond network was found in hydrogenated nanodiamonds dispersions compared to dispersions of nanodiamonds with other surface terminations. Although no hydrogen bonds are formed between water and hydrogenated surface groups, a long-range disruption of the water hydrogen bond network is evidenced in hydrogenated nanodiamonds dispersion. We propose that this unusual hydration structure results from electron accumulation at the diamond–water interface.

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“…Solvated electrons in molecular cluster anions have been intriguing topics. − The solvated electron plays a prominent role in many important processes of physics, chemistry, and biochemistry. , In radiobiological physics and chemistry, the essentiality of the solvated electron has been revealed . The researchers in the quantum chemistry and molecular dynamics fields have found that an excess electron bound on either the cluster interior or the cluster surface exhibits different excess electron bound states including interior, surface, and network-permeating states. − The bound state of the excess electron influences the electronically excited-state relaxation dynamics, binding energies, as well as electronic and molecular spectra …”

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confidence: 99%

Role of Excess Electrons in Nonlinear Optical Response

Zhong

et al. 2015

J. Phys. Chem. Lett.

194

115

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The excess electron is a kind of special anion with dispersivity, loosely bounding and with other fascinating features, which plays a pivotal role (promote to about 10(6) times in (H2O)3{e}) in the large first hyperpolarizabilities (β0) of dipole-bound electron clusters. This discovery opens a new perspective on the design of novel nonlinear optical (NLO) molecular materials for electro-optic device application. Significantly, doping alkali metal atoms in suitable complexants was proposed as an effective approach to obtain electride and alkalide molecules with excess electron and large NLO responses. The first hyperpolarizability is related to the characteristics of complexants and the excess electron binding states. Subsequently, a series of new strategies for enhancing NLO response and electronic stability of electride and alkalide molecules are exhibited by using various complexants. These strategies include not only the behaviors of pushed and pulled electron, size, shape, and number of coordination sites of complexants but also the number and spin state of excess electrons in these unusual NLO molecules.

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Infrared Spectroscopy of Water Cluster Anions, (H₂O)_n=3‐24^‐ in the HOH Bending Region: Persistence of the Double H‐Bond Acceptor (AA) Water Molecule in the Excess Electron Binding Site of the Class I Isomers.

Abstract: Excess Electron Binding Site of the Class I Isomers. -(ROSCIOLI, J. R.; HAMMER, N. I.; JOHNSON*, M. A.; J. Phys. Chem. A 110 (2006) 24, 7517-7520; Sterling Chem. Lab., Yale Univ., New Haven, CT 06511, USA; Eng.) -Schramke 35-002 O) -n=3-24

Cited by 8 publications

References 1 publication

Thermal Equilibration Controls H-Bonding and the Vertical Detachment Energy of Water Cluster Anions

Thermal Equilibration Controls H-Bonding and the Vertical Detachment Energy of Water Cluster Anions

Unusual Water Hydrogen Bond Network around Hydrogenated Nanodiamonds

Role of Excess Electrons in Nonlinear Optical Response

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