Assessing MP2 frozen natural orbitals in relativistic correlated electronic structure calculations

Yuan, Xiang; Visscher, Lucas; Severo Pereira Gomes, Andre

Document type :

Autre communication scientifique (congrès sans actes - poster - séminaire...): Communication dans un congrès avec actes: Conférence invitée

Title :

Assessing MP2 frozen natural orbitals in relativistic correlated electronic structure calculations

Author(s) :

Yuan, Xiang [Orateur]
Physico-Chimie Moléculaire Théorique [PCMT]
Visscher, Lucas [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Severo Pereira Gomes, Andre [Auteur]

Physico-Chimie Moléculaire Théorique [PCMT]

Conference title :

Webinar...a way to REHE2022

City :

Online

Country :

Italie

Start date of the conference :

2021-11-25

Publication date :

2021-11-25

HAL domain(s) :

Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

The O(N6 high computational cost is a bottleneck preventing performing Coupled-Cluster (CC) on large systems, particularly when employing 4-component based relativistic Hamiltonians, for which in practice one ...
Show more >The O(N6 high computational cost is a bottleneck preventing performing Coupled-Cluster (CC) on large systems, particularly when employing 4-component based relativistic Hamiltonians, for which in practice one often uses uncontracted basis setgenerating large virtual molecular orbital (VMO) spaces.The canonical Hartree-Fock (HF) orbitals are not the most compact representation for post HF method. Alternative, using natural orbitals is an efficient way to reduce the orbital spacewhile retaining accuracy. We therefore implemented the MP2 frozen natural orbital (FNO) method [1] in the Exacorr code [2], with the particularity that our implementation can generate both complex and quaternion FNOs, and also express these in AO basis. It also allows us to obtain CCSD natural orbitals on AO basis, which can be subsequently used in analysis.We have investigated the orbital truncation errors for both correlation energy (at CCSD(T) level) and molecular properties (at CCSD level) such as theelectric field gradients at the nuclei (EFGs ), dipole and quadrupole momentsfor hydrogen halides HX (X=F, Cl, Br, I, At, Ts. We find that using FNOs accelerates the convergence of the correlation energy in a roughly uniform manner across the periodic table and that,with VMO spaces truncated to around half of the complete ones, we obtain reliable estimates for both energies and molecular properties in the complete VMO spaces.[1] T. L. Barr, E. R. Davidson, Phys. Rev. A 1970, 1, 644; A. G. Taube, R. J. Bartlett, J. Chem. Phys. 2008, 128, 164101[2]J. V. Pototschnig, A. Papadopoulos, D. I. Lyakh, M. Repisky, L. Halbert, A. S. P. Gomes, H- J Aa. Jensen, L. Visscher, J. Chem. Theory. Comput. 2021, 17, 5509Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

Physiques et Chimie de l'Environnement Atmosphérique
ULNE

Collections :

Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL

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