Saved in:
| Main Authors: | , , , |
|---|---|
| Format: | Preprint |
| Published: |
2026
|
| Subjects: | |
| Online Access: | https://arxiv.org/abs/2605.14611 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866910221187678208 |
|---|---|
| author | Szczuczko, Lena Szczuczko, Julia Gałyńska, Marta Boguslawski, Katharina |
| author_facet | Szczuczko, Lena Szczuczko, Julia Gałyńska, Marta Boguslawski, Katharina |
| contents | We present a flexible, automated, and basis-set insensitive domain-based charge-transfer (CT) decomposition framework that can be combined with any CI-type excited-state wavefunction. Our approach is not based on excited-state densities and allows the excited-state character to be dissected into local and domain-based CT excitations and measures the individual contributions to each excited state. To guarantee a broad applicability, we introduce two domain-accumulation strategies to translate hole-particle substitutions to domain-domain excitations: a strict domain partitioning and a weighted approach suitable for small molecules and a large number of domains. The performance of both schemes is assessed for inter- and intramolecular CT excitations and various basis sets using EOM-CCSD and its simplified counterpart EOM-pCCD+S. Most importantly, the CT character is, to a large extent, basis-set independent, and both domain-accumulation schemes give consistent results. Overall, our framework provides a robust CT analysis and a domain resolution of the excitation character for a variety of computational setups and excited-state models. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2605_14611 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | A Flexible, Automated, and Basis-Set Insensitive Domain-Based Charge-Transfer Decomposition for Correlated Wavefunctions and its Application to Inter- and Intramolecular Cases Szczuczko, Lena Szczuczko, Julia Gałyńska, Marta Boguslawski, Katharina Chemical Physics We present a flexible, automated, and basis-set insensitive domain-based charge-transfer (CT) decomposition framework that can be combined with any CI-type excited-state wavefunction. Our approach is not based on excited-state densities and allows the excited-state character to be dissected into local and domain-based CT excitations and measures the individual contributions to each excited state. To guarantee a broad applicability, we introduce two domain-accumulation strategies to translate hole-particle substitutions to domain-domain excitations: a strict domain partitioning and a weighted approach suitable for small molecules and a large number of domains. The performance of both schemes is assessed for inter- and intramolecular CT excitations and various basis sets using EOM-CCSD and its simplified counterpart EOM-pCCD+S. Most importantly, the CT character is, to a large extent, basis-set independent, and both domain-accumulation schemes give consistent results. Overall, our framework provides a robust CT analysis and a domain resolution of the excitation character for a variety of computational setups and excited-state models. |
| title | A Flexible, Automated, and Basis-Set Insensitive Domain-Based Charge-Transfer Decomposition for Correlated Wavefunctions and its Application to Inter- and Intramolecular Cases |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2605.14611 |