Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 135, Issue 11, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3636084
Keywords
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Funding
- l'Universite de Strasbourg (UdS)
- Natural Science Foundation (FNU) of the Danish Agency for Science, Technology, and Innovation
- University of Bonn
- Max Planck Institut
- [ANR-09-BLAN-0195 TEMAMA]
- [SFB 813]
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The spectrum arising from the (pi*)(2) configuration of the chalcogen dimers, namely, the X(2)1, a2, and b0(+) states, is calculated using wave-function theory based methods. Two-component (2c) and four-component (4c) multireference configuration interaction (MRCI) and Fock-space coupled cluster (FSCC) methods are used as well as two-step methods spin-orbit complete active space perturbation theory at 2nd order (SO-CASPT2) and spin-orbit difference dedicated configuration interaction (SO-DDCI). The energy of the X(2)1 state corresponds to the zero-field splitting of the ground state spin triplet. It is described with high accuracy by the 2- and 4-component methods in comparison with experiment, whereas the two-step methods give about 80% of the experimental values. The b0(+) state is well described by 4c-MRCI, SO-CASPT2, and SO-DDCI, but FSCC fails to describe this state and an intermediate Hamiltonian FSCC ansatz is required. The results are readily rationalized by a two-parameter model; Delta epsilon, the pi* spinor splitting by spin-orbit coupling and K, the exchange integral between the pi(1)* and the pi(-1)* spinors with, respectively, angular momenta 1 and -1. This model holds for all systems under study with the exception of Po-2. (C) 2011 American Institute of Physics. [doi:10.1063/1.3636084]
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