Active Spaces and Non-Orthogonal Configuration Interaction Approaches for Investigating Molecules on Metal Surfaces

Autor:	Junhan Chen, Wenjie Dou, Joseph Subotnik
Rok vydání:	2022
Předmět:	Chemical Physics (physics.chem-ph) Physics - Chemical Physics FOS: Physical sciences Physics::Chemical Physics Physical and Theoretical Chemistry Computer Science Applications
Zdroj:	Journal of Chemical Theory and Computation. 18:7321-7335
ISSN:	1549-9626 1549-9618
DOI:	10.1021/acs.jctc.2c00740
Popis:	We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like wavefunction where frontier orbitals are allowed to be nonorthogonal versus (ii) a fully non-orthogonal configuration interaction wavefunction based on constrained Hartree-Fock states. We test both the strong and weak metal-molecule hybridization ($\Gamma$) limits as well as the strong and weak electron-electron repulsion (U) limits. We obtain accurate results as compared with exact numerical renormalization group (NRG) theory, recovering charge transfer states where appropriate. The current framework should open a path to run molecular non-adiabatic dynamics on metal surfaces.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::3ada79cc2b7cc826f7e33b553aaf7184 https://doi.org/10.1021/acs.jctc.2c00740 Zobrazit plný text záznamu