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Communication Dans Un Congrès Année : 2019

Relativistic equation of motion coupled cluster based on four-compoment Hamiltonians

Methods based on the coupled cluster ansatz and employing four-component Hamiltonians are particularly appealing in treating the electronic structure of molecules containing heavy centers, due to their ecient treatment of electron correlation and spin-orbit coupling (SOC) [1] on the same footing, up to and including the superheavy elements, as well as to serve as benchmark to more approximate relativistic Hamiltonians, notably those where SOC is treated more approximately (see for instance [2] and references therein). In this contribution we discuss our recent implementation [3] in the Dirac program [4] of the equation of motion coupled cluster method for excitation energies (EOM-EE-CCSD), single electron attachment (EOM-EA-CCSD) and single electron detachment (EOM-IPCCSD). We showcase the method by addressing the determination of the low-lying states of oxide radicals of group 17 elements (XO, X = Cl, Br, I, At, Ts), the excited and ionized states of the PuO2 molecule in the gas phase [5], as well as the ionization energies of halide ions in water droplets [6]. In the latter case, we use the frozen density embedding approach to combine EOM-IP-CCSD (for the halogens) and the SAOP model potential (for the water molecules) to determine the ionization energies for the complete halide droplet system, while sampling di fferent nuclear confi gurations with snapshots obtained from classical molecular dynamics simulations with polarizable force fields [7]. This work has been supported by the French national agency for research, contract ANR-11-LABX-0005 chemical and physical properties of the atmosphere (CaPPA). References 1. T. Fleig, Chem. Phys., 2 (2012) 395 ; T. Saue, ChemPhysChem, 12 (2011) 3077 2. E. Epifanovsky et al, J. Phys. Chem., 143 (2015) 064102 ; Z. Cao, Z. Li, F. Wang, W. Liu, Phys. Chem. Chem. Phys., 19 (2017) 3713 ; L. Cheng, F. Wang, J. F. Stanton, J. Gauss, J. Phys. Chem., 148 (2018) 044108 3. A. Shee, T. Saue, L. Visscher, A. S. P. Gomes, J. Phys. Chem., 149 (2018) 174113 4. http://diracprogram.org 5. S. Kervazo, F. Real, F. Virot, A. S. P. Gomes, V. Vallet arXiv:1906.03157 (2019) 6. Y. Bouchafra, A. Shee, F. Real, V. Vallet, A. S. P. Gomes Phys. Rev. Lett., 121 (2018) 266001 7. F. Real et al, J. Chem. Phys., 144, (2016) 124513

Yassine Bouchafra
  • Fonction : Auteur
  • PersonId : 1038372
Loïc Halbert
  • Fonction : Auteur
  • PersonId : 1032011
Florent Réal
Avijit Shee
  • Fonction : Auteur
  • PersonId : 983041
Trond Saue
Lucas Visscher
  • Fonction : Auteur
  • PersonId : 933548
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hal-02157296 , version 1 (16-06-2019)

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  • HAL Id : hal-02157296 , version 1

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Yassine Bouchafra, Loïc Halbert, Florent Réal, Valérie Vallet, François Virot, et al.. Relativistic equation of motion coupled cluster based on four-compoment Hamiltonians. ISTCP 2019 - 10th Triennial Congress of the International Society for Theoretical Chemical Physics, Jul 2019, Tromsø, Norway. ⟨hal-02157296⟩
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