An ab initio and experimental study of bromine on low-temperature water clusters and ice surfaces

Ramondo, Fabio; Sodeau, John R.; Roddis, Tristan B.; Williams, Neil

doi:10.1039/b001379j

Cited by 20 publications

(45 citation statements)

References 42 publications

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“…Con- sistent with this, we do not see a measurable perturbation of the Raman profile of the water vibrations by the presence of bromine in the solution, despite the large vibrational shifts predicted in the complex. 11 The poor mechanical coupling between Br 2 and water, yet the observation of a frequency red-shift that is larger than in the tightly bound 1:1 complex, suggests that the vibrational shift is due to dielectric solvation. The effect can be understood as the increased polarizability of Br 2 due to lowering of its ion-pair states by dielectric solvation, a model that has previously been advanced to explain many-body systematics of vibrational shifts and interactions in halogens and hydrogen halides.…”

Section: Solvation Of Br 2 In Water: Quenching Of Rrmentioning

confidence: 99%

“…In optimized structures of 2-8 water units, Br 2 is both oxygen and hydrogen bonded to the water network, sometimes with multiple bonds on the same Br atom. [10][11][12] The turnaround in the interaction character from the 1:1 complex to bulk water makes bromine an interesting solute for interrogating hydration. Here, we rely on the information content in Raman spectra of Br 2 and Br 3 − , to make inferences about local structure and dynamics of hydration.…”

Section: Introductionmentioning

confidence: 99%

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Solvation dynamics through Raman spectroscopy: Hydration of Br2 and Br3−, and solvation of Br2 in liquid bromine

Branigan

Halberstadt

Apkarian

2011

The Journal of Chemical Physics

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Raman spectroscopy of bromine in the liquid phase and in water illustrates uncommon principles and yields insights regarding hydration. In liquid Br(2), resonant excitation over the B((3)Π(0u)(+)) ← X((1)Σ(g)(+)) valence transition at 532 nm produces a weak resonant Raman (RR) progression accompanied by a five-fold stronger non-resonant (NR) scattering. The latter is assigned to pre-resonance with the C-state, which in turn must be strongly mixed with inter-molecular charge transfer states. Despite the electronic resonance, RR of Br(2) in water is quenched. At 532 nm, the homogeneously broadened fundamental is observed, as in the NR case at 785 nm. The implications of the quenching of RR scattering are analyzed in a simple, semi-quantitative model, to conclude that the inertial evolution of the Raman packet in aqueous Br(2) occurs along multiple equivalent water-Br(2) coordinates. In distinct contrast with hydrophilic hydration in small clusters and hydrophobic hydration in clathrates, it is concluded that the hydration shell of bromine in water consists of dynamically equivalent fluxional water molecules. At 405 nm, the RR progression of Br(3)(-) is observed, accompanied by difference transitions between the breathing of the hydration shell and the symmetric stretch of the ion. The RR scattering process in this case can be regarded as the coherent photo-induced electron transfer to the solvent and its radiative back-transfer.

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Section: Solvation Of Br 2 In Water: Quenching Of Rrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solvation dynamics through Raman spectroscopy: Hydration of Br2 and Br3−, and solvation of Br2 in liquid bromine

Branigan

Halberstadt

Apkarian

2011

The Journal of Chemical Physics

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“…Naturally, the electron distribution pattern of the added solute plays the key role to shape up the structure of the water network around the solute. Several experiment, theory, and simulation studies are reported in the literature to understand the structure and dynamics of microhydration on neutral and charged chemical species for their unique spectroscopic and thermodynamic properties. − The properties of these solute embedded water clusters provide basic understanding of the fundamental interactions those are responsible for hydration process at molecular level and thus it is important not only to chemists but also to physicists, biologists and material scientists.…”

Section: Introductionmentioning

confidence: 99%

How Much Water Is Needed To Ionize Formic Acid?

Maity

2013

J. Phys. Chem. A

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Structure, molecular properties, energy parameters, and vibrational IR spectra of hydrated clusters of formic acid (FOH), FOH·nH2O (n = 1-8), are presented following first principle based electronic structure theory. Several geometrical arrangements are considered as initial guess structures to look for the minimum energy equilibrium structures applying ωB97X-D density functional and aug-cc-pVDZ set of atomic basis functions. Results on FOH-water clusters suggest that the most stable structure of formic acid exists as a charge-separated ion pair, FO(-δ)---H(+δ)---O(-δ)H2, in hydrated clusters, FOH·nH2O, for cluster size n ≥ 7. The calculated interaction energy between FOH and the solvent water cluster increases significantly by adding the seventh solvent water molecule to the FOH·6H2O cluster whereas the solvent stabilization energy of FOH increases continuously on successive addition of solvent water molecules (n = 1-8). Energy partitioning of the solvent stabilization energy of FOH·nH2O clusters suggests an electrostatic component of energy to play the major role in solvent stability and does depict sudden variation for n = 7. Formation of a charge-separated ion pair for cluster size n ≥ 7 is manifested in simulated IR spectra of FOH·nH2O clusters. Static polarizabilities of hydrated formic acid clusters are calculated and observed to vary linearly with the size of the clusters, suggesting reliability in prediction of polarizability for larger size hydrated clusters of formic acid.

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“…This is due to the strong interaction between the electrons from one of the oxygen lone pair orbitals and the empty σ * orbital of the halogen molecules which is pointing outward along the dihalogen axis. This makes the oxygen and the two halogen atoms collinear, as established by microwave 10,11 and infrared spectroscopies [12][13][14] and confirmed by ab initio calculations. [9][10][11][14][15][16] Using the analogy with the (stronger) hydrogen bond, this specific bonding has been called "halogen bond."…”

Section: A Theoretical Simulation Of the Resonant Raman Spectroscopy mentioning

confidence: 60%

A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes

Franklin-Mergarejo

Rubayo‐Soneira

Halberstadt

et al. 2016

The Journal of Chemical Physics

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The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice.

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An ab initio and experimental study of bromine on low-temperature water clusters and ice surfaces

Cited by 20 publications

References 42 publications

Solvation dynamics through Raman spectroscopy: Hydration of Br2 and Br3−, and solvation of Br2 in liquid bromine

Solvation dynamics through Raman spectroscopy: Hydration of Br2 and Br3−, and solvation of Br2 in liquid bromine

How Much Water Is Needed To Ionize Formic Acid?

A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes

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