Benchmarking two-photon absorption with CC3 quadratic response theory, and comparison with density-functional response theory

Martin Paterson, O Christiansen, F Pawlowski, P Jorgensen, C Hattig, T Helgaker, P Salek

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Abstract

We present a detailed study of the effects of electron correlation on two-photon absorption calculated by coupled cluster quadratic response theory. The hierarchy of coupled cluster models CCS, CC2, CCSD, and CC3 has been used to investigate the effects of electron correlation on the two-photon absorption cross sections of formaldehyde (CH2O), diacetylene (C4H2), and water (H2O). In particular, the effects of triple excitations on two-photon transition cross sections are determined for the first time. In addition, we present a detailed comparison of the coupled cluster results with those obtained from Hartree-Fock and density-functional response theories. We have investigated the local-density approximation, the pure Becke-Lee-Yang-Parr (BLYP) functional, the hybrid Becke-3-parameter-Lee-Yang-Parr (B3LYP), and the Coulomb-attenuated B3LYP (CAM-B3LYP) functionals. Our results show that the CAM-B3LYP functional, when used in conjuction with a one-particle basis-set containing diffuse functions, has much promise; however, care must still be exercised for diffuse Rydberg-type states. (c) 2006 American Institute of Physics.

Original languageEnglish
Article number054322
Pages (from-to)-
Number of pages10
JournalJournal of Chemical Physics
Volume124
Issue number5
DOIs
Publication statusPublished - 7 Feb 2006

Keywords

  • FULL CONFIGURATION-INTERACTION
  • COUPLED-CLUSTER CALCULATIONS
  • FREQUENCY-DEPENDENT POLARIZABILITIES
  • MULTIPHOTON TRANSITION MOMENTS
  • PROBABILITY RATE CONSTANTS
  • TRIPLES MODEL CC3
  • CROSS-SECTIONS
  • 1ST HYPERPOLARIZABILITIES
  • EXCITATION-ENERGIES
  • SINGLET OXYGEN

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