Production and photodetachment of stoichiometric sodium chloride cluster anions

Yang, Y. A.; Conover, C. W. S.; Bloomfield, L. A.

doi:10.1016/0009-2614(89)87335-x

Cited by 42 publications

(22 citation statements)

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“…3,14,15 Although reliable and informative, the experimental measurements cannot determine the geometrical structure of the anion or neutral species. In contrast, theoretical treatments, especially ab initio methods, are able to provide precise information about the origin of the electron binding by describing the potential responsible for it.…”

Section: Binding Of An Excess Electron To Sodium Chloridementioning

confidence: 99%

“…Earlier, this group reported the value of 1.25 ( 0.01 eV by means of their photodetachment threshold measurements on sodium chloride cluster anions in the plume of laser-vaporized sodium chloride. 14 The experimental VDE ) 1.55 eV seems more reliable in the context of simulated annealing results providing 1.58 eV 3 and 1.59 eV. 5 In addition, Yu et al 5 found that both simulated annealing and local minimization techniques yield a slightly bent head-to-tail chain as the minimum energy structure for the anionic (NaCl) 2 -cluster.…”

Section: (Nacl) 2 - the Current Statusmentioning

confidence: 99%

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First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

2003

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The possibility of electron binding to sodium chloride dimers in the gas-phase was studied at the coupled cluster level with single, double, and noniterative triple excitations using aug-cc-pVDZ+6s6p4d basis sets. It was found that three kinds of anions can be formedsquasi-linear dipole-bound, nearly rhombic quadrupolebound, and linear solvated-electron anions. In contrast to the earlier results, it was found that the rhombic neutral dimer (which is the neutral global minimum) does bind an excess electron to form an electronically stable anion of quadrupole nature. The global minimum on the ground-state anionic potential energy surface corresponds to the dipole-bound anion of quasi-linear structure (NaCl‚‚‚NaCl) -whose vertical electron binding energy is 12 051 cm -1 . It was also found that solvated-electron structure (ClNa‚‚‚NaCl) -is considerably higher in energy than the anionic global minimum but its vertical electron detachment energy is significantly larger (i.e., 21 306 cm -1 ). The nearly rhombic (NaCl) 2 -lies only 0.181 eV above the anionic global minimum but below the global minimum of the neutral species.

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Section: Binding Of An Excess Electron To Sodium Chloridementioning

confidence: 99%

Section: (Nacl) 2 - the Current Statusmentioning

confidence: 99%

First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

2003

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“…30 Meanwhile, the larger spatial dimensions of alkali thiocyanate clusters could result in separations large enough for excess charges and lead to the formation of multiply charged anion (MCA) clusters, which have not been observed for alkali halide salt clusters. [9][10][11][12][13][14][15][16][17] The formation of MCAs in return could attract cations and accelerate nucleation and crystal growth. Third, alkali halide cluster anions M n X − n+1 (where M is an alkali metal atom and X is a halogen atom) have been discovered possessing electron binding energies higher than any atomic anions and have been named superhalogen anions.…”

Section: Introductionmentioning

confidence: 99%

“…Electronic mail: xuebin.wang@pnnl.gov level information of crystal nucleation and growth is still largely unknown, and most experimental studies are performed at the macro-or mesoscopic scale because there are few experimental methods which approach the atomic scale in solutions or vapors. So far, there have been few relevant experiments performed on alkali halide clusters in the gas phase, produced by laser ablation on solid salt samples; these studies employed mass spectrometry, ion mobility measurements, and photodetachment photoelectron spectroscopy [9][10][11][12][13][14][15][16][17] and have provided very useful information about structural evolution in the early growth stage of alkali halide salts. Compared to experiments, molecular dynamics and Monte Carlo simulations have been developed and used for decades to study nucleation, and a large number of studies have been carried out using computer simulations.…”

Section: Introductionmentioning

confidence: 99%

Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

2015

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Due to the fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford the formation of supersaturated droplets and generation of various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle, witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged Mx(SCN)x+1(-), doubly charged My(SCN)y+2(2-) (M = Na, K), and triply charged Kz(SCN)z+3(3-) anion clusters (x, y, and z stand for the number of alkali atoms in the singly, doubly, and triply charged clusters, respectively) were produced via electrospray of the corresponding salt solutions and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for the sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions Mx(SCN)x+1(-) (M = Na and K) demonstrate that they are superhalogen anions. The existence of doubly charged anions My(SCN)y+2(2-) (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions Kz(SCN)z+3(3-) (z = 3x, x ≥ 6) was initially discovered from the photoelectron spectra for those singly charged anions of Mx(SCN)x+1(-) with the same mass-to-charge ratio (m/z), and later independently confirmed by the observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters were found to become preferred, but at higher temperatures, those multiply charged clusters were suppressed. The series of anion clusters investigated here range from molecular-like M1(SCN)2(-) to nano-sized K22(SCN)25(3-), providing a vivid molecular-level growth pattern reflecting the initial salt nucleation process.

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“…1 Recently, extensive studies have been done on clusters with excess electrons. [2][3][4][5][6][7][8][9][10][11][12] In addition to the intrinsic interest as an important class of molecular ions, clusters with excess electrons begin to exhibit some of the electron accommodation mechanisms of the bulk solid as their sizes increase. For example, excess electrons can localize at anion vacancies to form F centers.…”

Section: Introductionmentioning

confidence: 99%

Structure and electron localization of anionic NaCl clusters with excess electrons

Xia

Bloomfield

et al. 1995

The Journal of Chemical Physics

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The structure and electron localization mode of ͑NaCl͒ n Ϫ clusters with a single excess electron are studied with simulated annealing. We find that the attachment of the excess electron induces a dramatic reorganization of the ionic configuration. The electron is localized in most clusters, either in an F-center state or partially neutralizing a sodium ion sticking out of the cluster. In rare cases the electron is found to be delocalized, spreading over the surface of the cluster. The calculated electron binding energies agree very well with recent photoelectron measurements.

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Production and photodetachment of stoichiometric sodium chloride cluster anions

Cited by 42 publications

References 7 publications

First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

Structure and electron localization of anionic NaCl clusters with excess electrons

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Production and photodetachment of stoichiometric sodium chloride cluster anions

Cited by 42 publications

References 7 publications

First Evidence of Rhombic (NaCl)2‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

First Evidence of Rhombic (NaCl)2‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

Probing the early stages of salt nucleation—Experimental and theoretical investigations of sodium/potassium thiocyanate cluster anions

Structure and electron localization of anionic NaCl clusters with excess electrons

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First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.

First Evidence of Rhombic (NaCl)₂^‐. Ab initio Reexamination of the Sodium Chloride Dimer Anion.