A systematic theoretical investigation of the lowest valence- and Rydberg-excited singlet states of trans-butadiene. The character of the 1 1Bu(V) state revisited

Michal Dallos, Hans Lischka

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39 Scopus citations

Abstract

In the present work systematic procedures for the balanced description of the lowest singlet excited valence and Rydberg states of butadiene, especially for the correct description of the 11Bu, state, are presented. In the first step of the calculation averaged natural orbitals (ANOs) were computed from the density matrices of the ground state, the 2 1Ag and the 11Bu states. For the 11Bu state the configuration interaction (CI) wave function used for the computation of the respective density matrix contained all possible single and double excitations from the 1bg(π) orbital into all virtual orbitals and double excitations describing σ-π electron correlation. For the ground and 21Ag states a standard multireference (MR) CI with singles and doubles (CISD)/complete-active- space (CAS)(4,4) wave function was used. In the second step, these ANOs were used in extended MR-CISD, MR-CISD with Davidson correction and MR averaged quadratic coupled cluster calculations. This scheme was also extended to state-averaging including the four lowest Rydberg states 11B g(3s), 11Au(3pσ), 2 1Au(3pσ) and 21B u(3pπ). Our best value for the vertical excitation energy to the 11Bu state is 6.18 eV, close to previous equation-of-motion coupled-cluster with singles and doubles including noniterative triples [EOM - CCSD (T̃)] and complete-active-space perturbation theory to second order (CASPT2) results, but significantly lower than most of the previous MR-CI and MR-CI based results. The computed vertical excitation energy to the 21Ag state of 6.55 eV is significantly below previous EOM-CCSD(T) and EOM - CCSD (T̃) results and demonstrates the deficiencies of these methods in the case of MR situations. On the other hand, this excitation energy is larger than previous CASPT2 results for the 21Ag state. The character of the 1 1Bu state is predominantly of valence character, but is more diffuse than the ground state. 〈x2〉 values for the 11Bu state range between 25.4 and 26.3a0 2 in the three-state calculations.

Original languageEnglish
Pages (from-to)16-26
Number of pages11
JournalTheoretical Chemistry Accounts
Volume112
Issue number1
DOIs
StatePublished - Apr 2004

Keywords

  • Ab initio multireference calculations
  • Multireference configuration interaction with singles and doubles and multireference averaged quadratic coupled cluster
  • Rydberg and valence states
  • Valence character of the 1B state

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