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The Journal of Chemical Physics : Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz

By Kerstin Klein and Jürgen Gauss

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Book Id: WPLBN0002169487
Format Type: PDF eBook :
File Size: Serial Publication
Reproduction Date: 18 November 2008

Title: The Journal of Chemical Physics : Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz  
Author: Kerstin Klein and Jürgen Gauss
Volume: Issue : November 2008
Language: English
Subject: Science, Physics, Natural Science
Collections: Periodicals: Journal and Magazine Collection (Contemporary), The Journal of Chemical Physics Collection
Historic
Publication Date:
Publisher: American Institute of Physics

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And Jürgen Gauss, K. K. (n.d.). The Journal of Chemical Physics : Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz. Retrieved from http://gejl.org/


Description
Description: Spin-orbit splittings for 2Π states are calculated within coupled-cluster (CC) theory via first-order degenerate perturbation theory. Using the equation-of-motion CC variant for ionization potentials (EOMIP-CC), the two components of the considered 2Π state are treated in a balanced way by generating both radical states via annihilation of one electron out of the CC wave function of the corresponding anion. We report on the implementation of the described approach within the CC singles and doubles approximation. To ensure computational efficiency, an atomic mean-field approximation for the spin-orbit integrals is used, resulting in a formulation in terms of one-electron transition-density matrices. Calculations for XH radicals (X = O, S, Se) lead to satisfactory agreement with experiment. For 2Π systems that within an EOMIP-CC treatment can only be reached from a triplet reference state (e.g., CF and O2+) the influence of spin contamination is found to be negligible.

 
 



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