{ital Ab initio} study of the dipole-bound anion (H{sub 2}O{hor_ellipsis}HCl){sup {minus}}

Journal Article · Sun Aug 01 04:00:00 EDT 1999 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.479614· OSTI ID:357268

Skurski, P ^[1]; Gutowski, M ^[2]

---

1. Department of Chemistry, University of Gdansk, 80-952 Gdansk (Poland)
2. Materials Resources, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)

The (H{sub 2}O{hor_ellipsis}HCl){sup {minus}} anion has been studied at the coupled cluster level of theory with single, double, and noniterative, triple excitations whereas lowest energy structures have been determined at the second-order Mo/ller{endash}Plesset level. The vertical electron detachment energy and the adiabatic electron affinity were found to be 475 and 447 cm{sup {minus}1}, respectively, and they agree very well with the maximum of the dominant peak in the photoelectron spectrum of (H{sub 2}O{hor_ellipsis}HCl){sup {minus}} at 436 cm{sup {minus}1}, recorded by Bowen and collaborators. Our results indicate that electron correlation contributions to the electron binding energy are important and represent {approximately}70{percent} of its total value. Both for the neutral and the anion, the two equivalent C{sub s} symmetry minima are separated by a C{sub 2v} transition state and the energy barrier amounts to only 77 cm{sup {minus}1}. Thus the equilibrium structures averaged over vibrations are effectively planar (C{sub 2v}). The Franck{endash}Condon (FC) factors, calculated in harmonic approximation, indicate that the neutral complex formed in photoelectron spectroscopy (PES) experiments may be vibrationally excited in both soft intermolecular and stiff intramolecular modes. The theoretical photoelectron spectrum based on the calculated FC factors is compared to the experimental PES spectrum of Bowen {ital et al.} {copyright} {ital 1999 American Institute of Physics.}

• OSTI ID: 357268
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 111; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
AFFINITY
ANIONS
BINDING ENERGY
ELECTRON ATTACHMENT
ELECTRON CORRELATION
ELECTRON DETACHMENT
ELECTRONEGATIVITY
FRANCK-CONDON PRINCIPLE
HYDROCHLORIC ACID
HYDROGEN BURNING
HYDROGEN COMPOUNDS
MOLECULAR CLUSTERS
PHOTOELECTRON SPECTROSCOPY
WATER