Quantum Monte Carlo calculations of electronic excitation energies: the case of the singlet n to pi* (CO) transition in acrolein - Sorbonne Université Access content directly
Book Sections Year : 2011

Quantum Monte Carlo calculations of electronic excitation energies: the case of the singlet n to pi* (CO) transition in acrolein

Abstract

We report state-of-the-art quantum Monte Carlo calculations of the singlet $n \to \pi^*$ (CO) vertical excitation energy in the acrolein molecule, extending the recent study of Bouabça {\it et al.} [J. Chem. Phys. {\bf 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.
Fichier principal
Vignette du fichier
acrolein.pdf (130.94 Ko) Télécharger le fichier
Origin Files produced by the author(s)
Loading...

Dates and versions

hal-00550057 , version 1 (23-12-2010)

Identifiers

Cite

Julien Toulouse, Michel Caffarel, Peter Reinhardt, Philip E. Hoggan, C. J. Umrigar. Quantum Monte Carlo calculations of electronic excitation energies: the case of the singlet n to pi* (CO) transition in acrolein. P. E. Hoggan, J. Maruani, P. Piecuch, G. Delgado-Barrio and E. J. Brandas. Advances in the Theory of Quantum Systems in Chemistry and Physics, Springer, pp.343-351, 2011, Progress in Theoretical Chemistry and Physics, Vol. 22, ⟨10.1007/978-94-007-2076-3⟩. ⟨hal-00550057⟩
724 View
216 Download

Altmetric

Share

Gmail Mastodon Facebook X LinkedIn More