The ethylene 1 1B1u V state revisited

Thomas Müller, Michal Dallos, Hans Lischka

Research output: Contribution to journalArticle

78 Scopus citations

Abstract

We describe a general procedure to resolve the problem of artifical valence/Rydberg mixing encountered in ab initio CI calculations on the V(1 1B1u) state of ethylene. Davidson and McMurchie realized that the key to this problem are orbitals which adequately represent the V state. A two-step procedure is proposed, in which the first step focuses on generating appropriate molecular orbitals and the second step aims to describe the electron correlation quantitatively. A series of the currently most extensive MCSCF, MR-CISD, and MR-AQCC calculations for basis sets up to quadruple zeta quality and up to 80 million configurations are presented. Size extensivity corrections turn out to be crucial for highly accurate excitation energies. Our best estimate for the N- V state excitation energy of 7.7 eV lies between the experimental absorption maximum of 7.66 eV and a vibrationally corrected value of 7.8 eV. Hence, we do not find it necessary to refer to nonadiabatic effects in order to achieve agreement with the experimental data. The V state is characterized by its spatial extent, measured through the expectation value 〈x2〉, where x is the out-of-plane direction. With 16.5-17.0a02 it has a strong valence character, as compared to ≈90a020 for the 2 1B1u Rydberg state and 11.7a02 for the ground state.

Original languageEnglish
Pages (from-to)7176-7184
Number of pages9
JournalJournal of Chemical Physics
Volume110
Issue number15
DOIs
StatePublished - Apr 15 1999

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