Quantum Monte Carlo Calculations of Electronic Excitation Energies: The Case of the Singlet n→π (CO) Transition in Acrolein

  • Julien Toulouse
  • Michel Caffarel
  • Peter Reinhardt
  • Philip E. Hoggan
  • C. J. Umrigar
Part of the Progress in Theoretical Chemistry and Physics book series (PTCP, volume 22)


We report state-of-the-art quantum Monte Carlo calculations of the singlet n→π (CO) vertical excitation energy in the acrolein molecule, extending the recent study of Bouabça et al. (J Chem Phys 130:114107, 2009). We investigate the effect of using a Slater basis set instead of a Gaussian basis set, and of using state-average versus state-specific complete-active-space (CAS) wave functions, with or without reoptimization of the coefficients of the configuration state functions (CSFs) and of the orbitals in variational Monte Carlo (VMC). It is found that, with the Slater basis set used here, both state-average and state-specific CAS(6,5) wave functions give an accurate excitation energy in diffusion Monte Carlo (DMC), with or without reoptimization of the CSF and orbital coefficients in the presence of the Jastrow factor. In contrast, the CAS(2,2) wave functions require reoptimization of the CSF and orbital coefficients to give a good DMC excitation energy. Our best estimates of the vertical excitation energy are between 3.86 and 3.89 eV.


Quantum Monte Carlo Slater Basis Trial Wave Function Vertical Excitation Energy Diffusion Monte Carlo 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



Most QMC calculations have been done on the IBM Blue Gene of Forschungszentrum Jülich (Germany) within the DEISA project STOP-Qalm. CJU acknowledges support from NSF grant number CHE-1004603.


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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Julien Toulouse
    • 1
  • Michel Caffarel
    • 2
  • Peter Reinhardt
    • 1
  • Philip E. Hoggan
    • 3
  • C. J. Umrigar
    • 4
  1. 1.Laboratoire de Chimie ThéoriqueUniversité Pierre et Marie Curie and CNRSParisFrance
  2. 2.Laboratoire de Chimie et Physique Quantiques, IRSAMCCNRS and Université de ToulouseToulouseFrance
  3. 3.LASMEACNRS and Université Blaise PascalAubièreFrance
  4. 4.Laboratory of Atomic and Solid State PhysicsCornell UniversityIthacaUSA

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