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Title: Probing electronic wave functions of sodium-doped clusters: Dyson orbitals, anisotropy parameters, and ionization cross-sections

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1]
  1. Univ. of Southern California, Los Angeles, CA (United States)
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We apply high-level ab initio methods to describe the electronic structure of small clusters of ammonia and dimethylether (DME) doped with sodium, which provide a model for solvated electrons. We investigate the effect of the solvent and cluster size on the electronic states. We consider both energies and properties, with a focus on the shape of the electronic wave function and the related experimental observables such as photoelectron angular distributions. The central quantity in modeling photoionization experiments is the Dyson orbital, which describes the difference between the initial N-electron and final (N-1)-electron states of a system. Dyson orbitals enter the expression of the photoelectron matrix element, which determines total and partial photoionization cross-sections. We compute Dyson orbitals for the Na(NH3)n and Na(DME)m clusters using correlated wave functions (obtained with equation-of-motion coupled-cluster model for electron attachment with single and double substitutions) and compare them with more approximate Hartree-Fock and Kohn-Sham orbitals. As a result, we also analyze the effect of correlation and basis sets on the shapes of Dyson orbitals and the experimental observables.

Research Organization:
Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-05ER15685
OSTI ID:
1332003
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (6)

Vacuum ultraviolet photoionization cross section of the hydroxyl radical journal May 2018
Calculations of non-adiabatic couplings within equation-of-motion coupled-cluster framework: Theory, implementation, and validation against multi-reference methods journal January 2018
Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation journal January 2018
Autocorrelation of electronic wave-functions: a new approach for describing the evolution of electronic structure in the course of dynamics journal May 2018
Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation text January 2018
Autocorrelation of electronic wave-functions: a new approach for describing the evolution of electronic structure in the course of dynamics text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
solvated electrons
Dyson orbitals
photoionization cross-sections
photoelectron angular distributions
theoretical modeling
assessment of DFT functionals
EOM-EA-CCSD
equation-of-motion coupled-clusters theory