Projected Atomic Orbitals As Optimal Virtual Space for Excited State Projection-Based Embedding Calculations.
J Chem Theory Comput
; 20(9): 3420-3425, 2024 May 14.
Article
in En
| MEDLINE
| ID: mdl-38626416
ABSTRACT
The projected atomic orbital (PAO) technique is presented for the construction of virtual orbital spaces in projection-based embedding (PbE) applications. The proposed straightforward procedure produces a set of virtual orbitals that are used in the final, high-level calculation of the embedded active subsystem. The PAO scheme is demonstrated on intermolecular potentials of bimolecular complexes in ground and excited states, including Rydberg excitations. The results show the outstanding performance of the PbE method when used with PAO virtual orbitals compared with those produced using common orbital localization techniques. The good agreement of the resulting PbE potential curves with those from high-level ab initio dimer calculations, also in diffuse basis sets, confirms that the PAO technique can be suggested for future applications using top-down embedding methods.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Chem Theory Comput
Year:
2024
Document type:
Article
Affiliation country:
Hungary