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Title: Transition properties from the Hermitian formulation of the coupled cluster polarization propagator

Theory of one-electron transition density matrices has been formulated within the time-independent coupled cluster method for the polarization propagator [R. Moszynski, P. S. ┼╗uchowski, and B. Jeziorski, Coll. Czech. Chem. Commun. 70, 1109 (2005)]. Working expressions have been obtained and implemented with the coupled cluster method limited to single, double, and linear triple excitations (CC3). Selected dipole and quadrupole transition probabilities of the alkali earth atoms, computed with the new transition density matrices are compared to the experimental data. Good agreement between theory and experiment is found. The results obtained with the new approach are of the same quality as the results obtained with the linear response coupled cluster theory. The one-electron density matrices for the ground state in the CC3 approximation have also been implemented. The dipole moments for a few representative diatomic molecules have been computed with several variants of the new approach, and the results are discussed to choose the approximation with the best balance between the accuracy and computational efficiency.
Authors:
; ;  [1]
  1. Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)
Publication Date:
OSTI Identifier:
22308893
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; APPROXIMATIONS; ATOMS; COMPARATIVE EVALUATIONS; DENSITY MATRIX; DIPOLE MOMENTS; DIPOLES; EFFICIENCY; ELECTRON DENSITY; ELECTRONS; EXCITATION; GROUND STATES; MOLECULES; POLARIZATION