Theoretical study of the dipole-bound anion (H{sub 2}O{hor_ellipsis}NH{sub 3}){sup {minus}}

Journal Article · Wed Apr 01 04:00:00 EST 1998 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.476037· OSTI ID:625391

Skurski, P ^[1]; Gutowski, M ^[2]

---

1. Department of Chemistry, University of Gdansk, 80-952Gdansk (Poland)
2. Solid State Theory Group, Materials and Chemical Sciences, Pacific Northwest National Laboratory, Richland, Washington99352 (United States)

The adiabatic electron detachment energy for (H{sub 2}O{hor_ellipsis}NH{sub 3}){sup {minus}} has been found to be 109cm{sup {minus}1} at the coupled-cluster level of theory with single, double, and noninteractive triple excitations (CCSD(T)), to be compared with the recent experimental result of 123{endash}129cm{sup {minus}1} obtained by Abdoul-Carime {ital et al.} [Z. Phys. D {bold 40}, 55 (1997)]. The stationary points on the potential energy surface of the neutral and anionic dimer have been determined at the second-order Mo/ller-Plesset level of theory. Our results indicate that the second-order dispersion interaction between the loosely bound electron and electrons of the neutral dimer is as important as the electrostatic electron-dipole stabilization. The higher-order electron correlation corrections are also very important and the CCSD(T) electron binding energy is approximately four times larger than the Koopmans theorem estimation. In addition, the hydrogen bond in H{sub 2}O{hor_ellipsis}NH{sub 3} is susceptible to a deformation upon attachment of an electron. This deformation enhances both the electrostatic and dispersion components of the electron binding energy. The calculated Franck-Condon factors indicate that neutral dimers formed in electron photodetachment experiments may be vibrationally excited in both soft intermolecular and stiff intramolecular modes. The theoretical photoelectron spectrum based on the calculated Franck-Condon factors is reported. {copyright} {ital 1998 American Institute of Physics.}

• OSTI ID: 625391
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 108; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
AMMONIA
ANIONS
BINDING ENERGY
BOUND STATE
ELECTRON CORRELATION
ELECTRON DETACHMENT
FRANCK-CONDON PRINCIPLE
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
WATER