{"doi":"10.1021/acs.jpclett.3c00545","title":"Excimer Energies","abstract":"A multistate energy decomposition analysis (MS-EDA) method is introduced for excimers using density functional theory. Although EDA has been widely applied to intermolecular interactions in the ground state, few methods are currently available for excited-state complexes. Here, the total energy of an excimer state is separated into exciton excitation energy Δ E Ex (|Ψ X ·Ψ Y ⟩*), resulting from the state interaction between locally excited monomer states |Ψ X * ·Ψ Y ⟩ and |Ψ X ·Ψ Y * ⟩, a superexchange stabilization energy Δ E SE, originating from the mutual charge transfer between two monomers |Ψ X + ·Ψ Y ⟩ and |Ψ X – ·Ψ Y + ⟩, and an orbital-and-configuration delocalization term Δ E OCD due to the expansion of configuration space and block-localized orbitals to the fully delocalized dimer system. Although there is no net charge transfer in symmetric excimer cases, the resonance of charge-transfer states is critical to stabilizing the excimer. The monomer localized excited and charge-transfer states are variationally optimized, forming a minimal active space for nonorthogonal state interaction (NOSI) calculations in multistate density functional theory to yield the intermediate states for energy analysis. The present MS-EDA method focuses on properties unique to excited states, providing insights into exciton coupling, superexchange and delocalization energies. MS-EDA is illustrated on the acetone and pentacene excimer systems; three configurations of the latter case are examined, including the optimized excimer, a stacked configuration of two pentacene molecules and the fishbone orientation. It is found that excited-state energy splitting is strongly dependent on the relative energies of the monomer excited states and the phase-matching of the monomer wave functions.","journal":"The Journal of Physical Chemistry Letters","year":2023,"id":337045,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":18,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9566,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":483725,"name":"Christian Hettich","orcid":null,"position":1,"is_corresponding":false},{"id":908975,"name":"Jun Zhang","orcid":"0000-0001-9093-9430","position":2,"is_corresponding":false},{"id":234183,"name":"Meiyi Liu","orcid":null,"position":3,"is_corresponding":false},{"id":231460,"name":"Jiali Gao","orcid":"0000-0003-0106-7154","position":4,"is_corresponding":false},{"id":709296,"name":"Ruoqi Zhao","orcid":"0000-0003-3921-9790","position":0,"is_corresponding":true}],"reference_count":93,"raw_metadata":null,"created_at":"2026-07-19T01:10:21.947540Z","pmid":"36929896","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}