Solvatochromic shifts from coupled-cluster theory embedded in density functional theory.

Abstract : : Building on the framework recently reported for determining general response properties for frozen-density embedding [S. Höfener, A. S. P. Gomes, and L. Visscher, J. Chem. Phys. 136, 044104 (2012)], in this work we report a first implementation of an embedded coupled-cluster in density-functional theory (CC-in-DFT) scheme for electronic excitations, where only the response of the active subsystem is taken into account. The formalism is applied to the calculation of coupled-cluster excitation energies of water and uracil in aqueous solution. We find that the CC-in-DFT results are in good agreement with reference calculations and experimental results. The accuracy of calculations is mainly sensitive to factors influencing the correlation treatment (basis set quality, truncation of the cluster operator) and to the embedding treatment of the ground-state (choice of density functionals). This allows for efficient approximations at the excited state calculation step without compromising the accuracy. This approximate scheme makes it possible to use a first principles approach to investigate environment effects with specific interactions at coupled-cluster level of theory at a cost comparable to that of calculations of the individual subsystems in vacuum.
Type de document :
Article dans une revue
Journal of Chemical Physics, American Institute of Physics, 2013, 139 (10), pp.104106. 〈10.1063/1.4820488〉
Liste complète des métadonnées

https://hal.archives-ouvertes.fr/hal-00873300
Contributeur : Andre Gomes <>
Soumis le : mardi 15 octobre 2013 - 14:26:18
Dernière modification le : mardi 3 juillet 2018 - 11:46:46

Identifiants

Collections

Citation

Sebastian Höfener, Andre Severo Pereira Gomes, Lucas Visscher. Solvatochromic shifts from coupled-cluster theory embedded in density functional theory.. Journal of Chemical Physics, American Institute of Physics, 2013, 139 (10), pp.104106. 〈10.1063/1.4820488〉. 〈hal-00873300〉

Partager

Métriques

Consultations de la notice

56