Photoelectron spectroscopy of doubly charged anions: Intramolecular Coulomb repulsion and solvent stabilization

Journal Article · Thu Nov 05 04:00:00 EST 1998 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp982698x· OSTI ID:316001

Ding, C F; Wang, X B; Wang, L S ^[1]

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1. Washington State Univ., Richland, WA (United States). Dept. of Physics

Photoelectron spectroscopy has been combined with an electrospray ionization technique to study gas-phase multiple charged anions and their intramolecular Coulomb repulsion and solvation stabilization. The authors report an initial study on a series of linear dicarboxylate dianions (DC{sup 2{minus}}), {sup {minus}}O{sub 2}C(CH{sub 2}){sub n}CO{sub 2}{sup {minus}} (n = 3--6), solvated by one and two waters. The second electron binding energy of DC{sup 2{minus}} decreases with decreasing aliphatic chain length owing to the increasing Coulomb repulsion between the two charges; the dianion with n = 2 has a binding energy close to zero and is not stable in the gas phase. The authors found that this dianion can be stabilized by one water, and in general the first water stabilizes the electron binding energy of DC{sup 2{minus}} by {approximately}0.3 eV. The second water, however, was observed to show a much stronger stabilization effect ({approximately}0.6 eV), suggesting that the two waters solvate the two carboxylate groups separately.

• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: AC06-76RL01830
• OSTI ID: 316001
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 45 Vol. 102; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ANIONS
BINDING ENERGY
CHEMICAL PROPERTIES
COULOMB FIELD
ELECTRONS
PHOTOELECTRON SPECTROSCOPY
SOLVATION
WATER