Extending orbital-optimized density functional theory to L-edge XPS and beyond: Spin-orbit coupling via non-orthogonal quasi-degenerate perturbation theory Article Swipe
Richard Kang
,
Leonardo A. Cunha
,
Diptarka Hait
,
Martin Head‐Gordon
·
YOU?
·
· 2025
· Open Access
·
· DOI: https://doi.org/10.48550/arxiv.2505.14570
YOU?
·
· 2025
· Open Access
·
· DOI: https://doi.org/10.48550/arxiv.2505.14570
Quantum mechanical calculations of core electron binding energies (CEBEs) leading to 2p hole states are relevant to interpreting L-edge x-ray photo-electron spectroscopy (XPS), as well as higher edges. Orbital-optimized density functional theory (OO-DFT) accurately predicts K-edge CEBEs but is challenged by the presence of significant spin-orbit coupling (SOC) at L- and higher edges. To extend OO-DFT to L-edges and higher, our method utilizes scalar-relativistic, spin-restricted OO-DFT to construct a minimal, quasi-degenerate basis of core-hole states corresponding to a chosen inner-shell (e.g. ionizing all six possible 2p spin orbitals). Non-orthogonal configuration interaction (NOCI) is then used to make the matrix elements of the full Hamiltonian including SOC in this quasi-degenerate model space of determinants. Using a screened 1-electron SOC operator parametrized with the Dirac-Coulomb-Breit (DCB) Hamiltonian results in doublet splitting (DS) values for 3rd row atoms that are nearly in quantitative agreement with experiment. The resulting NOCI eigenvalues are shifted by the average of the (scalar) OO-DFT CEBEs to yield CEBEs (split by SOC) corrected for dynamic correlation. Comparing calculations on gas phase molecules with experimental results establishes that NO-QDPT with the SCAN functional (NO-QDPT/SCAN), using the DCB screened 1-electron SOC operator is accurate to about 0.2 eV for L-edge CEBEs of molecules containing 3rd row atoms. However, this NO-QDPT approach becomes less accurate for 4th-row elements starting in the middle of the 3d transition metal series, especially as the atomic number increases.
Related Topics
Concepts
No concepts available.
Metadata
- Type
- preprint
- Language
- en
- Landing Page
- http://arxiv.org/abs/2505.14570
- https://arxiv.org/pdf/2505.14570
- OA Status
- green
- OpenAlex ID
- https://openalex.org/W4415024537
All OpenAlex metadata
Raw OpenAlex JSON
- OpenAlex ID
-
https://openalex.org/W4415024537Canonical identifier for this work in OpenAlex
- DOI
-
https://doi.org/10.48550/arxiv.2505.14570Digital Object Identifier
- Title
-
Extending orbital-optimized density functional theory to L-edge XPS and beyond: Spin-orbit coupling via non-orthogonal quasi-degenerate perturbation theoryWork title
- Type
-
preprintOpenAlex work type
- Language
-
enPrimary language
- Publication year
-
2025Year of publication
- Publication date
-
2025-05-20Full publication date if available
- Authors
-
Richard Kang, Leonardo A. Cunha, Diptarka Hait, Martin Head‐GordonList of authors in order
- Landing page
-
https://arxiv.org/abs/2505.14570Publisher landing page
- PDF URL
-
https://arxiv.org/pdf/2505.14570Direct link to full text PDF
- Open access
-
YesWhether a free full text is available
- OA status
-
greenOpen access status per OpenAlex
- OA URL
-
https://arxiv.org/pdf/2505.14570Direct OA link when available
- Cited by
-
0Total citation count in OpenAlex
Full payload
| id | https://openalex.org/W4415024537 |
|---|---|
| doi | https://doi.org/10.48550/arxiv.2505.14570 |
| ids.doi | https://doi.org/10.48550/arxiv.2505.14570 |
| ids.openalex | https://openalex.org/W4415024537 |
| fwci | |
| type | preprint |
| title | Extending orbital-optimized density functional theory to L-edge XPS and beyond: Spin-orbit coupling via non-orthogonal quasi-degenerate perturbation theory |
| biblio.issue | |
| biblio.volume | |
| biblio.last_page | |
| biblio.first_page | |
| topics[0].id | https://openalex.org/T11809 |
| topics[0].field.id | https://openalex.org/fields/16 |
| topics[0].field.display_name | Chemistry |
| topics[0].score | 0.994700014591217 |
| topics[0].domain.id | https://openalex.org/domains/3 |
| topics[0].domain.display_name | Physical Sciences |
| topics[0].subfield.id | https://openalex.org/subfields/1607 |
| topics[0].subfield.display_name | Spectroscopy |
| topics[0].display_name | Advanced NMR Techniques and Applications |
| topics[1].id | https://openalex.org/T10612 |
| topics[1].field.id | https://openalex.org/fields/25 |
| topics[1].field.display_name | Materials Science |
| topics[1].score | 0.994700014591217 |
| topics[1].domain.id | https://openalex.org/domains/3 |
| topics[1].domain.display_name | Physical Sciences |
| topics[1].subfield.id | https://openalex.org/subfields/2504 |
| topics[1].subfield.display_name | Electronic, Optical and Magnetic Materials |
| topics[1].display_name | Magnetism in coordination complexes |
| topics[2].id | https://openalex.org/T10002 |
| topics[2].field.id | https://openalex.org/fields/31 |
| topics[2].field.display_name | Physics and Astronomy |
| topics[2].score | 0.9936000108718872 |
| topics[2].domain.id | https://openalex.org/domains/3 |
| topics[2].domain.display_name | Physical Sciences |
| topics[2].subfield.id | https://openalex.org/subfields/3107 |
| topics[2].subfield.display_name | Atomic and Molecular Physics, and Optics |
| topics[2].display_name | Advanced Chemical Physics Studies |
| is_xpac | False |
| apc_list | |
| apc_paid | |
| language | en |
| locations[0].id | pmh:oai:arXiv.org:2505.14570 |
| locations[0].is_oa | True |
| locations[0].source.id | https://openalex.org/S4306400194 |
| locations[0].source.issn | |
| locations[0].source.type | repository |
| locations[0].source.is_oa | True |
| locations[0].source.issn_l | |
| locations[0].source.is_core | False |
| locations[0].source.is_in_doaj | False |
| locations[0].source.display_name | arXiv (Cornell University) |
| locations[0].source.host_organization | https://openalex.org/I205783295 |
| locations[0].source.host_organization_name | Cornell University |
| locations[0].source.host_organization_lineage | https://openalex.org/I205783295 |
| locations[0].license | cc-by-nc-nd |
| locations[0].pdf_url | https://arxiv.org/pdf/2505.14570 |
| locations[0].version | submittedVersion |
| locations[0].raw_type | text |
| locations[0].license_id | https://openalex.org/licenses/cc-by-nc-nd |
| locations[0].is_accepted | False |
| locations[0].is_published | False |
| locations[0].raw_source_name | |
| locations[0].landing_page_url | http://arxiv.org/abs/2505.14570 |
| locations[1].id | doi:10.48550/arxiv.2505.14570 |
| locations[1].is_oa | True |
| locations[1].source.id | https://openalex.org/S4306400194 |
| locations[1].source.issn | |
| locations[1].source.type | repository |
| locations[1].source.is_oa | True |
| locations[1].source.issn_l | |
| locations[1].source.is_core | False |
| locations[1].source.is_in_doaj | False |
| locations[1].source.display_name | arXiv (Cornell University) |
| locations[1].source.host_organization | https://openalex.org/I205783295 |
| locations[1].source.host_organization_name | Cornell University |
| locations[1].source.host_organization_lineage | https://openalex.org/I205783295 |
| locations[1].license | |
| locations[1].pdf_url | |
| locations[1].version | |
| locations[1].raw_type | article |
| locations[1].license_id | |
| locations[1].is_accepted | False |
| locations[1].is_published | |
| locations[1].raw_source_name | |
| locations[1].landing_page_url | https://doi.org/10.48550/arxiv.2505.14570 |
| indexed_in | arxiv, datacite |
| authorships[0].author.id | https://openalex.org/A5000146195 |
| authorships[0].author.orcid | https://orcid.org/0000-0001-8901-1723 |
| authorships[0].author.display_name | Richard Kang |
| authorships[0].author_position | first |
| authorships[0].raw_author_name | Kang, Richard |
| authorships[0].is_corresponding | False |
| authorships[1].author.id | https://openalex.org/A5058939274 |
| authorships[1].author.orcid | https://orcid.org/0000-0003-2671-2375 |
| authorships[1].author.display_name | Leonardo A. Cunha |
| authorships[1].author_position | middle |
| authorships[1].raw_author_name | Cunha, Leonardo A. |
| authorships[1].is_corresponding | False |
| authorships[2].author.id | https://openalex.org/A5034530544 |
| authorships[2].author.orcid | https://orcid.org/0000-0003-1570-920X |
| authorships[2].author.display_name | Diptarka Hait |
| authorships[2].author_position | middle |
| authorships[2].raw_author_name | Hait, Diptarka |
| authorships[2].is_corresponding | False |
| authorships[3].author.id | https://openalex.org/A5015311244 |
| authorships[3].author.orcid | https://orcid.org/0000-0002-4309-6669 |
| authorships[3].author.display_name | Martin Head‐Gordon |
| authorships[3].author_position | last |
| authorships[3].raw_author_name | Head-Gordon, Martin |
| authorships[3].is_corresponding | False |
| has_content.pdf | True |
| has_content.grobid_xml | True |
| is_paratext | False |
| open_access.is_oa | True |
| open_access.oa_url | https://arxiv.org/pdf/2505.14570 |
| open_access.oa_status | green |
| open_access.any_repository_has_fulltext | False |
| created_date | 2025-10-10T00:00:00 |
| display_name | Extending orbital-optimized density functional theory to L-edge XPS and beyond: Spin-orbit coupling via non-orthogonal quasi-degenerate perturbation theory |
| has_fulltext | False |
| is_retracted | False |
| updated_date | 2025-11-06T06:51:31.235846 |
| primary_topic.id | https://openalex.org/T11809 |
| primary_topic.field.id | https://openalex.org/fields/16 |
| primary_topic.field.display_name | Chemistry |
| primary_topic.score | 0.994700014591217 |
| primary_topic.domain.id | https://openalex.org/domains/3 |
| primary_topic.domain.display_name | Physical Sciences |
| primary_topic.subfield.id | https://openalex.org/subfields/1607 |
| primary_topic.subfield.display_name | Spectroscopy |
| primary_topic.display_name | Advanced NMR Techniques and Applications |
| cited_by_count | 0 |
| locations_count | 2 |
| best_oa_location.id | pmh:oai:arXiv.org:2505.14570 |
| best_oa_location.is_oa | True |
| best_oa_location.source.id | https://openalex.org/S4306400194 |
| best_oa_location.source.issn | |
| best_oa_location.source.type | repository |
| best_oa_location.source.is_oa | True |
| best_oa_location.source.issn_l | |
| best_oa_location.source.is_core | False |
| best_oa_location.source.is_in_doaj | False |
| best_oa_location.source.display_name | arXiv (Cornell University) |
| best_oa_location.source.host_organization | https://openalex.org/I205783295 |
| best_oa_location.source.host_organization_name | Cornell University |
| best_oa_location.source.host_organization_lineage | https://openalex.org/I205783295 |
| best_oa_location.license | cc-by-nc-nd |
| best_oa_location.pdf_url | https://arxiv.org/pdf/2505.14570 |
| best_oa_location.version | submittedVersion |
| best_oa_location.raw_type | text |
| best_oa_location.license_id | https://openalex.org/licenses/cc-by-nc-nd |
| best_oa_location.is_accepted | False |
| best_oa_location.is_published | False |
| best_oa_location.raw_source_name | |
| best_oa_location.landing_page_url | http://arxiv.org/abs/2505.14570 |
| primary_location.id | pmh:oai:arXiv.org:2505.14570 |
| primary_location.is_oa | True |
| primary_location.source.id | https://openalex.org/S4306400194 |
| primary_location.source.issn | |
| primary_location.source.type | repository |
| primary_location.source.is_oa | True |
| primary_location.source.issn_l | |
| primary_location.source.is_core | False |
| primary_location.source.is_in_doaj | False |
| primary_location.source.display_name | arXiv (Cornell University) |
| primary_location.source.host_organization | https://openalex.org/I205783295 |
| primary_location.source.host_organization_name | Cornell University |
| primary_location.source.host_organization_lineage | https://openalex.org/I205783295 |
| primary_location.license | cc-by-nc-nd |
| primary_location.pdf_url | https://arxiv.org/pdf/2505.14570 |
| primary_location.version | submittedVersion |
| primary_location.raw_type | text |
| primary_location.license_id | https://openalex.org/licenses/cc-by-nc-nd |
| primary_location.is_accepted | False |
| primary_location.is_published | False |
| primary_location.raw_source_name | |
| primary_location.landing_page_url | http://arxiv.org/abs/2505.14570 |
| publication_date | 2025-05-20 |
| publication_year | 2025 |
| referenced_works_count | 0 |
| abstract_inverted_index.a | 68, 77, 114 |
| abstract_inverted_index.2p | 11, 85 |
| abstract_inverted_index.3d | 222 |
| abstract_inverted_index.L- | 49 |
| abstract_inverted_index.To | 53 |
| abstract_inverted_index.as | 23, 25, 227 |
| abstract_inverted_index.at | 48 |
| abstract_inverted_index.by | 40, 149, 161 |
| abstract_inverted_index.eV | 196 |
| abstract_inverted_index.in | 106, 126, 138, 217 |
| abstract_inverted_index.is | 38, 92, 191 |
| abstract_inverted_index.of | 3, 43, 72, 100, 111, 152, 200, 220 |
| abstract_inverted_index.on | 169 |
| abstract_inverted_index.to | 10, 16, 56, 66, 76, 95, 157, 193 |
| abstract_inverted_index.0.2 | 195 |
| abstract_inverted_index.3rd | 132, 203 |
| abstract_inverted_index.DCB | 186 |
| abstract_inverted_index.SOC | 105, 117, 189 |
| abstract_inverted_index.The | 143 |
| abstract_inverted_index.all | 82 |
| abstract_inverted_index.and | 50, 58 |
| abstract_inverted_index.are | 14, 136, 147 |
| abstract_inverted_index.but | 37 |
| abstract_inverted_index.for | 131, 164, 197, 213 |
| abstract_inverted_index.gas | 170 |
| abstract_inverted_index.our | 60 |
| abstract_inverted_index.row | 133, 204 |
| abstract_inverted_index.six | 83 |
| abstract_inverted_index.the | 41, 97, 101, 121, 150, 153, 180, 185, 218, 221, 228 |
| abstract_inverted_index.(DS) | 129 |
| abstract_inverted_index.NOCI | 145 |
| abstract_inverted_index.SCAN | 181 |
| abstract_inverted_index.SOC) | 162 |
| abstract_inverted_index.core | 4 |
| abstract_inverted_index.full | 102 |
| abstract_inverted_index.hole | 12 |
| abstract_inverted_index.less | 211 |
| abstract_inverted_index.make | 96 |
| abstract_inverted_index.spin | 86 |
| abstract_inverted_index.that | 135, 177 |
| abstract_inverted_index.then | 93 |
| abstract_inverted_index.this | 107, 207 |
| abstract_inverted_index.used | 94 |
| abstract_inverted_index.well | 24 |
| abstract_inverted_index.with | 120, 141, 173, 179 |
| abstract_inverted_index.(DCB) | 123 |
| abstract_inverted_index.(SOC) | 47 |
| abstract_inverted_index.(e.g. | 80 |
| abstract_inverted_index.CEBEs | 36, 156, 159, 199 |
| abstract_inverted_index.Using | 113 |
| abstract_inverted_index.about | 194 |
| abstract_inverted_index.atoms | 134 |
| abstract_inverted_index.basis | 71 |
| abstract_inverted_index.metal | 224 |
| abstract_inverted_index.model | 109 |
| abstract_inverted_index.phase | 171 |
| abstract_inverted_index.space | 110 |
| abstract_inverted_index.using | 184 |
| abstract_inverted_index.x-ray | 19 |
| abstract_inverted_index.yield | 158 |
| abstract_inverted_index.(NOCI) | 91 |
| abstract_inverted_index.(XPS), | 22 |
| abstract_inverted_index.(split | 160 |
| abstract_inverted_index.K-edge | 35 |
| abstract_inverted_index.L-edge | 18, 198 |
| abstract_inverted_index.OO-DFT | 55, 65, 155 |
| abstract_inverted_index.atomic | 229 |
| abstract_inverted_index.atoms. | 205 |
| abstract_inverted_index.chosen | 78 |
| abstract_inverted_index.edges. | 27, 52 |
| abstract_inverted_index.extend | 54 |
| abstract_inverted_index.higher | 26, 51 |
| abstract_inverted_index.matrix | 98 |
| abstract_inverted_index.method | 61 |
| abstract_inverted_index.middle | 219 |
| abstract_inverted_index.nearly | 137 |
| abstract_inverted_index.number | 230 |
| abstract_inverted_index.states | 13, 74 |
| abstract_inverted_index.theory | 31 |
| abstract_inverted_index.values | 130 |
| abstract_inverted_index.(CEBEs) | 8 |
| abstract_inverted_index.4th-row | 214 |
| abstract_inverted_index.L-edges | 57 |
| abstract_inverted_index.NO-QDPT | 178, 208 |
| abstract_inverted_index.Quantum | 0 |
| abstract_inverted_index.average | 151 |
| abstract_inverted_index.becomes | 210 |
| abstract_inverted_index.binding | 6 |
| abstract_inverted_index.density | 29 |
| abstract_inverted_index.doublet | 127 |
| abstract_inverted_index.dynamic | 165 |
| abstract_inverted_index.higher, | 59 |
| abstract_inverted_index.leading | 9 |
| abstract_inverted_index.results | 125, 175 |
| abstract_inverted_index.series, | 225 |
| abstract_inverted_index.shifted | 148 |
| abstract_inverted_index.(OO-DFT) | 32 |
| abstract_inverted_index.(scalar) | 154 |
| abstract_inverted_index.However, | 206 |
| abstract_inverted_index.accurate | 192, 212 |
| abstract_inverted_index.approach | 209 |
| abstract_inverted_index.coupling | 46 |
| abstract_inverted_index.electron | 5 |
| abstract_inverted_index.elements | 99, 215 |
| abstract_inverted_index.energies | 7 |
| abstract_inverted_index.ionizing | 81 |
| abstract_inverted_index.minimal, | 69 |
| abstract_inverted_index.operator | 118, 190 |
| abstract_inverted_index.possible | 84 |
| abstract_inverted_index.predicts | 34 |
| abstract_inverted_index.presence | 42 |
| abstract_inverted_index.relevant | 15 |
| abstract_inverted_index.screened | 115, 187 |
| abstract_inverted_index.starting | 216 |
| abstract_inverted_index.utilizes | 62 |
| abstract_inverted_index.Comparing | 167 |
| abstract_inverted_index.agreement | 140 |
| abstract_inverted_index.construct | 67 |
| abstract_inverted_index.core-hole | 73 |
| abstract_inverted_index.corrected | 163 |
| abstract_inverted_index.including | 104 |
| abstract_inverted_index.molecules | 172, 201 |
| abstract_inverted_index.resulting | 144 |
| abstract_inverted_index.splitting | 128 |
| abstract_inverted_index.1-electron | 116, 188 |
| abstract_inverted_index.accurately | 33 |
| abstract_inverted_index.challenged | 39 |
| abstract_inverted_index.containing | 202 |
| abstract_inverted_index.especially | 226 |
| abstract_inverted_index.functional | 30, 182 |
| abstract_inverted_index.increases. | 231 |
| abstract_inverted_index.mechanical | 1 |
| abstract_inverted_index.orbitals). | 87 |
| abstract_inverted_index.spin-orbit | 45 |
| abstract_inverted_index.transition | 223 |
| abstract_inverted_index.Hamiltonian | 103, 124 |
| abstract_inverted_index.eigenvalues | 146 |
| abstract_inverted_index.establishes | 176 |
| abstract_inverted_index.experiment. | 142 |
| abstract_inverted_index.inner-shell | 79 |
| abstract_inverted_index.interaction | 90 |
| abstract_inverted_index.significant | 44 |
| abstract_inverted_index.calculations | 2, 168 |
| abstract_inverted_index.correlation. | 166 |
| abstract_inverted_index.experimental | 174 |
| abstract_inverted_index.interpreting | 17 |
| abstract_inverted_index.parametrized | 119 |
| abstract_inverted_index.quantitative | 139 |
| abstract_inverted_index.spectroscopy | 21 |
| abstract_inverted_index.configuration | 89 |
| abstract_inverted_index.corresponding | 75 |
| abstract_inverted_index.determinants. | 112 |
| abstract_inverted_index.Non-orthogonal | 88 |
| abstract_inverted_index.photo-electron | 20 |
| abstract_inverted_index.(NO-QDPT/SCAN), | 183 |
| abstract_inverted_index.spin-restricted | 64 |
| abstract_inverted_index.quasi-degenerate | 70, 108 |
| abstract_inverted_index.Orbital-optimized | 28 |
| abstract_inverted_index.Dirac-Coulomb-Breit | 122 |
| abstract_inverted_index.scalar-relativistic, | 63 |
| cited_by_percentile_year | |
| countries_distinct_count | 0 |
| institutions_distinct_count | 4 |
| citation_normalized_percentile |