Premium
Calculation of spectra and spin–spin coupling constants using a coupled–cluster polarization propagator method
Author(s) -
Geertsen Jan,
Oddershede Jens,
Scuseria Gustavo E.
Publication year - 1987
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560320746
Subject(s) - propagator , coupled cluster , coupling constant , excitation , atomic physics , polarization (electrochemistry) , cluster (spacecraft) , spectral line , physics , spin (aerodynamics) , chemistry , quantum mechanics , molecule , computer science , thermodynamics , programming language
Abstract We present a coupled‐cluster polarization propagator method based on a coupled cluster singles and doubles reference state. Applications to the Be atom show that we may calculate electronic excitation energies with an average absolute error of about 0.08 eV using this method. We have also calculated the nuclear spin–spin coupling constant of 1 H 19 F to be 524.4 cps, in good agreement with experiment. For Be there is a large effect of using coupled‐cluster rather than a low‐order Rayleigh–Schrödinger expansion, whereas the coupling constant of HF is less sensitive to this improvement in the reference state.