{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T12:47:29Z","timestamp":1792673249146,"version":"4.5.0"},"reference-count":89,"publisher":"American Chemical Society (ACS)","issue":"42","license":[{"start":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T00:00:00Z","timestamp":1791417600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T00:00:00Z","timestamp":1791417600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T00:00:00Z","timestamp":1791417600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100013145","name":"Chemical Sciences, Geosciences, and Biosciences Division","doi-asserted-by":"publisher","award":["DE-SC0023249"],"award-info":[{"award-number":["DE-SC0023249"]}],"id":[{"id":"10.13039\/100013145","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100013145","name":"Chemical Sciences, Geosciences, and Biosciences Division","doi-asserted-by":"publisher","award":["FWP 80818"],"award-info":[{"award-number":["FWP 80818"]}],"id":[{"id":"10.13039\/100013145","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100001388","name":"Wenner-Gren Foundation","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100001388","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,22]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We present a comprehensive experimental and computational spectroscopic study of the trinuclear cyanide-bridged mixed-valence complex trans-[RuIIL4{(\u03bc-NC)FeIII(CN)5}2]4\u2013 (FeRuFe), where L = pyridine or 4-methoxypyridine dissolved in methanol and water. Four complementary spectroscopies spanning 250 meV to 7.1 keV are combined to probe the electronic structure at all three metal sites. These include infrared, visible\/near IR, Ru L-edge, and Fe K-edge X-ray absorption spectroscopy probing the cyanide stretches, the metal-to-metal charge transfer transition, and electronic structure around the Ru and Fe atoms, respectively. The experimental spectra show that the two terminal Fe sites, which are crystallographically equivalent in the solid state, become inequivalent in solution. The IR spectra reveal that the solvent-exposed terminal cyanide broadens markedly in water relative to methanol. The solvation environment removes the degeneracy of the near IR metal-to-metal charge transfer transition and we measure two components separated by 190\u2013340 meV. A weak pre-edge feature at the Ru L3-edge, present in three of the four systems, reports on Fe\u2013Ru coupling through the cyanide bridge. To interpret the experimental spectra, we performed TDDFT calculations using complementary descriptions of the solvated complex. In one approach, the transition metal complex is treated quantum mechanically (QM) and the solvent is treated at the molecular mechanics (MM) level within a QM\/MM framework. We also performed targeted calculations in which molecules in the first solvation shell are included explicitly in the QM region along with the solute, while the remaining solvent is represented as background point charges taken from the QM\/MM force field. We find that core transitions localized at Fe or Ru sites are well reproduced within the QM\/MM framework, while spectroscopic observables sensitive to intersite coupling or specific solute\u2013solvent interactions benefit from explicit quantum mechanical treatment of the first solvation shell. This work establishes a systematic framework for simulating spectroscopic observables from the IR through the X-rays to characterize electronic coupling in multimetallic mixed-valence complexes mediated by the solvent.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c03779","type":"journal-article","created":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T15:01:50Z","timestamp":1791471710000},"page":"11211-11226","source":"Crossref","is-referenced-by-count":0,"title":["Comprehensive Experimental\nand Computational Spectroscopic\nStudy of Electronic Coupling in Solvated Mixed Valence Multimetal\nComplexes Using Photons from the IR through X-rays"],"prefix":"10.1021","volume":"130","author":[{"given":"Zhaoyuan","family":"Yang","sequence":"first","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0425-2101","authenticated-orcid":true,"given":"Amke","family":"Nimmrich","sequence":"additional","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6529-0905","authenticated-orcid":true,"given":"Amity","family":"Andersen","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99354"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daria V.","family":"Boglaienko","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99354"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2007-0319","authenticated-orcid":true,"given":"Benjamin I.","family":"Poulter","sequence":"additional","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenqing","family":"Cao","sequence":"additional","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elisa","family":"Biasin","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99352"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3625-366X","authenticated-orcid":true,"given":"Niranjan","family":"Govind","sequence":"additional","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]},{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99352"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6508-4124","authenticated-orcid":true,"given":"Munira","family":"Khalil","sequence":"additional","affiliation":[{"name":"University of Washington , , , ,","place":["Seattle, Washington, United States, 98195"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,8]]},"reference":[{"key":"2026102207420281000_cit1","doi-asserted-by":"publisher","first-page":"13148","DOI":"10.1021\/jp9605663","article-title":"Contemporary Issues in Electron Transfer\nResearch","volume":"100","author":"Barbara","year":"1996","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit2","doi-asserted-by":"publisher","first-page":"5663","DOI":"10.1021\/ic302331s","article-title":"Inorganic\nElectron Transfer: Sharpening a Fuzzy Border in Mixed Valency and\nExtending Mixed Valency across Supramolecular Systems","volume":"52","author":"Kubiak","year":"2013","journal-title":"Inorg. Chem."},{"key":"2026102207420281000_cit3","doi-asserted-by":"publisher","first-page":"3988","DOI":"10.1021\/ja01042a072","article-title":"Direct approach to measuring the Franck-Condon barrier to electron\ntransfer between metal ions","volume":"91","author":"Creutz","year":"1969","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit4","doi-asserted-by":"publisher","first-page":"X19","DOI":"10.1016\/S0020-1693(00)92059-0","article-title":"Electron transfer\nin mixed-valence compounds","volume":"40","author":"Meyer","year":"1980","journal-title":"Inorg. Chim. Acta"},{"key":"2026102207420281000_cit5","doi-asserted-by":"publisher","first-page":"5880","DOI":"10.1021\/ja0299506","article-title":"Molecular\nWires Built from Binuclear\nCyclometalated Complexes","volume":"125","author":"Fraysse","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit6","doi-asserted-by":"publisher","first-page":"11743","DOI":"10.1021\/ja104601b","article-title":"New Light-Harvesting\nMolecular Systems Constructed with a Ru(II) Complex and a Linear-Shaped\nRe(I) Oligomer","volume":"132","author":"Yamamoto","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit7","first-page":"247","volume-title":"Mixed Valence Chemistry-A\nSurvey and Classification","author":"Robin","year":"1968"},{"key":"2026102207420281000_cit8","doi-asserted-by":"publisher","first-page":"121","DOI":"10.1039\/cs9952400121","article-title":"Metal-metal\ninteractions in binuclear complexes exhibiting mixed valency; molecular\nwires and switches","volume":"24","author":"Ward","year":"1995","journal-title":"Chem. Soc. Rev."},{"key":"2026102207420281000_cit9","doi-asserted-by":"publisher","first-page":"3643","DOI":"10.1039\/a703504g","article-title":"Cyanide-bridged oligonuclear complexes:\nfeatures and attractions","author":"Vahrenkamp","year":"1997","journal-title":"J. Chem. Soc., Dalton\nTrans."},{"key":"2026102207420281000_cit10","doi-asserted-by":"publisher","first-page":"1676","DOI":"10.1016\/j.ccr.2012.10.018","article-title":"Electronic Coupling between Metal Ions in Cyanide-Bridged\nGround State and Excited State Mixed Valence Complexes","volume":"257","author":"Endicott","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"2026102207420281000_cit11","doi-asserted-by":"publisher","first-page":"4070","DOI":"10.1021\/ja963279l","article-title":"Orbital Specific Charge Transfer\nDistances, Solvent\nReorganization Energies, and Electronic Coupling Energies: Electronic\nStark Effect Studies of Parallel and Orthogonal Intervalence Transfer\nin (NC)5OsII-CN-RuIII(NH3)5\u2013","volume":"119","author":"Karki","year":"1997","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026102207420281000_cit12","doi-asserted-by":"publisher","first-page":"10637","DOI":"10.1021\/jp002549q","article-title":"Solvent Effects\non Vibrational Coherence and Ultrafast Reaction Dynamics in the Multicolor\nPump-Probe Spectroscopy of Intervalence Electron Transfer","volume":"104","author":"Kambhampati","year":"2000","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit13","doi-asserted-by":"publisher","first-page":"547","DOI":"10.1007\/BF01150847","article-title":"Spectroscopic Studies of Preferential and Asymmetric\nSolvation in Substituted Cyanoiron(II) Complexes","volume":"12","author":"Toma","year":"1983","journal-title":"J. Solution Chem."},{"key":"2026102207420281000_cit14","doi-asserted-by":"publisher","first-page":"2915","DOI":"10.1021\/jp953179m","article-title":"Influence\nof Solvent on the Spectroscopic Properties of Cyano Complexes of Ruthenium(II)","volume":"100","author":"Timpson","year":"1996","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit15","doi-asserted-by":"publisher","first-page":"1228","DOI":"10.1063\/1.464344","article-title":"Femtosecond\nExperiments and Absolute Rate Calculations on Intervalence Electron\nTransfer of Mixed-Valence Compounds","volume":"98","author":"Tominaga","year":"1993","journal-title":"J. Chem.\nPhys."},{"key":"2026102207420281000_cit16","doi-asserted-by":"publisher","first-page":"2609","DOI":"10.1021\/j100009a019","article-title":"Electronic\nCoherence, Vibrational Coherence, and Solvent Degrees of Freedom in\nthe Femtosecond Spectroscopy of Mixed-Valence Metal Dimers in H2O and D2O","volume":"99","author":"Reid","year":"1995","journal-title":"J. Phys. Chem.\nA"},{"key":"2026102207420281000_cit17","doi-asserted-by":"publisher","first-page":"177","DOI":"10.1016\/S0010-8545(00)00276-9","article-title":"The Effects of Electronic\nCoupling and Solvent Broadening\non the Intervalent Electron Transfer of a Centrosymmetric Mixed-Valence\nComplex","volume":"211","author":"Watson","year":"2001","journal-title":"Coord. Chem. Rev."},{"key":"2026102207420281000_cit18","doi-asserted-by":"publisher","first-page":"7718","DOI":"10.1021\/ic960489q","article-title":"Mixed-Valence Cyanopyridine-Bridged\nComplexes of Pentacyanoferrate and Pentaammineruthenium: Electronic\nStructure, Stability, and Redox Reactivity","volume":"35","author":"Almaraz","year":"1996","journal-title":"Inorg. Chem."},{"key":"2026102207420281000_cit19","doi-asserted-by":"publisher","first-page":"881","DOI":"10.1016\/S0010-8545(01)00383-6","article-title":"Advances\nin the Coordination Chemistry of [M(CN)5L]n\u2212 Ions (M = Fe, Ru, Os)","volume":"219\u2013221","author":"Baraldo","year":"2001","journal-title":"Coord. Chem. Rev."},{"key":"2026102207420281000_cit20","doi-asserted-by":"publisher","first-page":"16954","DOI":"10.1021\/ja507131q","article-title":"Molecular\nStructure, Spectroscopy,\nand Photoinduced Kinetics in Trinuclear Cyanide Bridged Complex in\nSolution: A First-Principles Perspective","volume":"136","author":"Zheng","year":"2014","journal-title":"J.\nAm. Chem. Soc."},{"key":"2026102207420281000_cit21","doi-asserted-by":"publisher","first-page":"4444","DOI":"10.1021\/jp401020j","article-title":"Simulating Ru L3-Edge\nX-ray Absorption Spectroscopy with Time-Dependent Density Functional\nTheory: Model Complexes and Electron Localization in Mixed-Valence\nMetal Dimers","volume":"117","author":"Van Kuiken","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit22","doi-asserted-by":"publisher","first-page":"5075","DOI":"10.1021\/acs.jpcb.7b12532","article-title":"Comprehensive Experimental\nand Computational Spectroscopic Study of Hexacyanoferrate Complexes\nin Water: From Infrared to X-ray Wavelengths","volume":"122","author":"Ross","year":"2018","journal-title":"J. Phys. Chem. B"},{"key":"2026102207420281000_cit23","doi-asserted-by":"publisher","first-page":"343","DOI":"10.1038\/s41557-020-00629-3","article-title":"Direct Observation\nof Coherent Femtosecond Solvent Reorganization Coupled to Intramolecular\nElectron Transfer","volume":"13","author":"Biasin","year":"2021","journal-title":"Nat. Chem."},{"key":"2026102207420281000_cit24","doi-asserted-by":"publisher","first-page":"378","DOI":"10.1021\/acs.jpclett.1c03613","article-title":"Femtosecond X-ray Spectroscopy Directly\nQuantifies Transient Excited-State Mixed Valency","volume":"13","author":"Liekhus-Schmaltz","year":"2022","journal-title":"J. Phys. Chem. Lett."},{"key":"2026102207420281000_cit25","doi-asserted-by":"publisher","first-page":"1306","DOI":"10.1021\/acs.jctc.3c01084","article-title":"Integrated Quantum-Classical\nProtocol\nfor the Realistic Description of Solvated Multinuclear Mixed-Valence\nTransition-Metal Complexes and Their Solvatochromic Properties","volume":"20","author":"Prampolini","year":"2024","journal-title":"J. Chem. Theory Comput."},{"key":"2026102207420281000_cit26","doi-asserted-by":"publisher","first-page":"6762","DOI":"10.1021\/ic0493649","article-title":"Fine Tuning of the\nElectronic Coupling between Metal Centers in Cyano-Bridged Mixed-Valent\nTrinuclear Complexes","volume":"43","author":"Albore\u0301s","year":"2004","journal-title":"Inorg. Chem."},{"key":"2026102207420281000_cit27","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.202500619","article-title":"Quantifying\nd\u2013d and Metal-Ligand\nInteractions across Distant Metal Sites as a Function of Ligand Architecture\nand Solvent","volume":"26","author":"Yang","year":"2025","journal-title":"ChemPhysChem"},{"key":"2026102207420281000_cit28","doi-asserted-by":"publisher","first-page":"033101","DOI":"10.1063\/1.5121853","article-title":"A versatile Johansson-type tender x-ray emission spectrometer","volume":"91","author":"Nowak","year":"2020","journal-title":"Rev. Sci. Instrum."},{"key":"2026102207420281000_cit29","doi-asserted-by":"publisher","first-page":"5001","DOI":"10.1021\/ja054932k","article-title":"Electronic and Molecular\nStructure of Photoexcited\n[RuII(bpy)3]2+ Probed by Picosecond X-ray Absorption Spectroscopy","volume":"128","author":"Gawelda","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit30","doi-asserted-by":"publisher","first-page":"503","DOI":"10.1107\/S1600577515005135","article-title":"The X-ray Pump-Probe instrument at\nthe Linac Coherent Light Source","volume":"22","author":"Chollet","year":"2015","journal-title":"J. Synchrotron\nRadiat."},{"key":"2026102207420281000_cit31","doi-asserted-by":"publisher","first-page":"040008","DOI":"10.1063\/1.4952880","article-title":"ePix100 camera:\nUse and applications at LCLS","volume":"1741","author":"Carini","year":"2016","journal-title":"AIP Conf. Proc."},{"key":"2026102207420281000_cit32","doi-asserted-by":"publisher","first-page":"608","DOI":"10.1107\/S1600577520004257","article-title":"The ePix10k 2-megapixel hard X-ray\ndetector at LCLS","volume":"27","author":"van Driel","year":"2020","journal-title":"J. Synchrotron Radiat."},{"key":"2026102207420281000_cit33","doi-asserted-by":"publisher","first-page":"6297","DOI":"10.1021\/ja964352a","article-title":"A Multiplet\nAnalysis of Fe K-Edge 1s \u2192 3d Pre-Edge\nFeatures of Iron Complexes","volume":"119","author":"Westre","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit34","doi-asserted-by":"publisher","DOI":"10.1063\/1.4901599","article-title":"A laboratory-based\nhard x-ray monochromator for high-resolution x-ray emission spectroscopy\nand x-ray absorption near edge structure measurements","volume":"85","author":"Seidler","year":"2014","journal-title":"Rev. Sci. Instrum."},{"key":"2026102207420281000_cit35","doi-asserted-by":"publisher","first-page":"537","DOI":"10.1107\/S0909049505012719","article-title":"ATHENA, ARTEMIS, HEPHAESTUS:\ndata analysis for X-ray\nabsorption spectroscopy using IFEFFIT","volume":"12","author":"Ravel","year":"2005","journal-title":"Synchrotron\nRadiat."},{"key":"2026102207420281000_cit36","doi-asserted-by":"publisher","first-page":"1477","DOI":"10.1016\/j.cpc.2010.04.018","article-title":"NWChem: A comprehensive\nand scalable open-source solution for large scale molecular simulations","volume":"181","author":"Valiev","year":"2010","journal-title":"Comput. Phys. Commun."},{"key":"2026102207420281000_cit37","doi-asserted-by":"publisher","first-page":"184102","DOI":"10.1063\/5.0004997","article-title":"NWChem:\nPast, present,\nand future","volume":"152","author":"Apra\u0300","year":"2020","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit38","doi-asserted-by":"publisher","first-page":"7077","DOI":"10.1021\/acs.jctc.3c00421","article-title":"NWChem: recent and ongoing developments","volume":"19","author":"Mejia-Rodriguez","year":"2023","journal-title":"J.\nChem. Theory Comput."},{"key":"2026102207420281000_cit39","doi-asserted-by":"publisher","first-page":"6158","DOI":"10.1063\/1.478522","article-title":"Toward reliable density functional\nmethods without\nadjustable parameters: The PBE0 model","volume":"110","author":"Adamo","year":"1999","journal-title":"J. Chem.\nPhys."},{"key":"2026102207420281000_cit40","doi-asserted-by":"publisher","first-page":"5639","DOI":"10.1063\/1.438980","article-title":"Contracted\nGaussian basis sets for molecular calculations.\nI. Second row atoms, Z = 11\u201318","volume":"72","author":"McLean","year":"1980","journal-title":"J. Chem.\nPhys."},{"key":"2026102207420281000_cit41","doi-asserted-by":"publisher","first-page":"650","DOI":"10.1063\/1.438955","article-title":"Self-consistent\nmolecular orbital methods. XX. A basis set for correlated wave functions","volume":"72","author":"Krishnan","year":"1980","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit42","doi-asserted-by":"publisher","first-page":"866","DOI":"10.1063\/1.452288","article-title":"Energy-adjusted ab\ninitio pseudopotentials for the first row transition elements","volume":"86","author":"Dolg","year":"1987","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit43","doi-asserted-by":"publisher","first-page":"123","DOI":"10.1007\/BF01114537","article-title":"Energy-adjusted ab initio pseudopotentials for the\nsecond and third row transition elements","volume":"77","author":"Andrae","year":"1990","journal-title":"Theor.\nChim. Acta"},{"key":"2026102207420281000_cit44","doi-asserted-by":"publisher","first-page":"1157","DOI":"10.1002\/jcc.20035","article-title":"Development\nand testing of a general amber force field","volume":"25","author":"Wang","year":"2004","journal-title":"J. Comput. Chem."},{"key":"2026102207420281000_cit45","doi-asserted-by":"publisher","first-page":"1255","DOI":"10.1021\/jp0363287","article-title":"Molecular Models of Hydroxide, Oxyhydroxide,\nand Clay Phases and the Development of a General Force Field","volume":"108","author":"Cygan","year":"2004","journal-title":"J. Phys. Chem. B"},{"key":"2026102207420281000_cit46","doi-asserted-by":"publisher","first-page":"6269","DOI":"10.1021\/j100308a038","article-title":"The missing term in effective pair\npotentials","volume":"91","author":"Berendsen","year":"1987","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit47","doi-asserted-by":"publisher","first-page":"1668","DOI":"10.1002\/jcc.20290","article-title":"The Amber biomolecular simulation\nprograms","volume":"26","author":"Case","year":"2005","journal-title":"J. Comput. Chem."},{"key":"2026102207420281000_cit48","doi-asserted-by":"publisher","first-page":"9020","DOI":"10.1021\/jp8001614","article-title":"Determination of Alkali and Halide\nMonovalent Ion Parameters for Use in Explicitly Solvated Biomolecular\nSimulations","volume":"112","author":"Joung","year":"2008","journal-title":"J. Phys. Chem. B"},{"key":"2026102207420281000_cit49","doi-asserted-by":"publisher","first-page":"327","DOI":"10.1016\/0021-9991(77)90098-5","article-title":"Numerical integration of the cartesian\nequations of motion of a system with constraints: molecular dynamics\nof n-alkanes","volume":"23","author":"Ryckaert","year":"1977","journal-title":"J. Comput. Phys."},{"key":"2026102207420281000_cit50","doi-asserted-by":"publisher","first-page":"3684","DOI":"10.1063\/1.448118","article-title":"Molecular\ndynamics with coupling to an external bath","volume":"81","author":"Berendsen","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit51","doi-asserted-by":"publisher","first-page":"1212","DOI":"10.1103\/PhysRevLett.76.1212","article-title":"Excitation Energies from Time-Dependent\nDensity-Functional Theory","volume":"76","author":"Petersilka","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"2026102207420281000_cit52","doi-asserted-by":"publisher","first-page":"291","DOI":"10.1016\/S0009-2614(99)01149-5","article-title":"Time-dependent\ndensity functional theory within the\nTamm-Dancoff approximation","volume":"314","author":"Hirata","year":"1999","journal-title":"Chem. Phys. Lett."},{"key":"2026102207420281000_cit53","doi-asserted-by":"publisher","first-page":"375","DOI":"10.1016\/S0009-2614(99)00137-2","article-title":"Time-dependent\ndensity functional theory for radicals:\nAn improved description of excited states with substantial double\nexcitation character","volume":"302","author":"Hirata","year":"1999","journal-title":"Chem. Phys. Lett."},{"key":"2026102207420281000_cit54","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-012-1124-z","article-title":"Segmented\ncontracted basis sets for\natoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q)","volume":"131","author":"Noro","year":"2012","journal-title":"Theor. Chem. Acc."},{"key":"2026102207420281000_cit55","doi-asserted-by":"publisher","first-page":"2257","DOI":"10.1063\/1.1677527","article-title":"Self-Consistent Molecular Orbital\nMethods. XII. Further Extensions of Gaussian-Type Basis Sets for Use\nin Molecular Orbital Studies of Organic Molecules","volume":"56","author":"Hehre","year":"1972","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit56","doi-asserted-by":"publisher","first-page":"3284","DOI":"10.1021\/ct3005613","article-title":"Linear-response and\nreal-time time-dependent density functional theory studies of core-level\nnear-edge x-ray absorption","volume":"8","author":"Lopata","year":"2012","journal-title":"J. Chem. Theory\nComput."},{"key":"2026102207420281000_cit57","doi-asserted-by":"publisher","first-page":"14680","DOI":"10.1039\/D2CP01132H","article-title":"Computational\nApproaches for XANES, VtC-XES, and RIXS\nUsing Linear-Response Time-Dependent Density Functional Theory Based\nMethods","volume":"24","author":"Nascimento","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026102207420281000_cit58","doi-asserted-by":"publisher","first-page":"9783","DOI":"10.1063\/1.467943","article-title":"Relativistic total\nenergy using regular approximations","volume":"101","author":"van Lenthe","year":"1994","journal-title":"J. Chem.\nPhys."},{"key":"2026102207420281000_cit59","doi-asserted-by":"publisher","first-page":"392","DOI":"10.1063\/1.476576","article-title":"Molecular density functional calculations in the regular\nrelativistic approximation: Method, application to coinage metal diatomics,\nhydrides, fluorides and chlorides, and comparison with first-order\nrelativistic calculations","volume":"109","author":"van Wu\u0308llen","year":"1998","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit60","doi-asserted-by":"publisher","first-page":"491","DOI":"10.1021\/ct8002892","article-title":"Gaussian basis set\nand planewave relativistic spin-orbit methods in NWChem","volume":"5","author":"Nichols","year":"2009","journal-title":"J. Chem. Theory Comput."},{"key":"2026102207420281000_cit61","doi-asserted-by":"publisher","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD: visual molecular dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Mol. Graphics"},{"key":"2026102207420281000_cit62","doi-asserted-by":"publisher","first-page":"3463","DOI":"10.1021\/ic950834w","article-title":"Red-Shifted\nCyanide Stretching Frequencies in Cyanide-Bridged Transition Metal\nDonor-Acceptor Complexes. Support for Vibronic Coupling","volume":"35","author":"Watzky","year":"1996","journal-title":"Inorg. Chem."},{"key":"2026102207420281000_cit63","doi-asserted-by":"publisher","first-page":"5260","DOI":"10.1021\/ic00051a018","article-title":"Electronic Coupling in Cyano-Bridged Ruthenium Polypyridine\nComplexes and Role of Electronic Effects on Cyanide Stretching Frequencies","volume":"31","author":"Bignozzi","year":"1992","journal-title":"Inorg. Chem."},{"key":"2026102207420281000_cit64","doi-asserted-by":"publisher","first-page":"4314","DOI":"10.1021\/jp993927y","article-title":"Ultrafast Infrared\nSpectroscopy of Vibrational States Prepared by Photoinduced Electron\nTransfer in (CN)5FeCNRu(NH3)5\u2013","volume":"104","author":"Wang","year":"2000","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit65","doi-asserted-by":"publisher","first-page":"2252","DOI":"10.1021\/jz200930h","article-title":"On the Role of High-Frequency\nIntramolecular Vibrations in Ultrafast Back-Electron Transfer Reactions","volume":"2","author":"Lynch","year":"2011","journal-title":"J. Phys. Chem. Lett."},{"key":"2026102207420281000_cit66","doi-asserted-by":"publisher","first-page":"241101","DOI":"10.1063\/1.4731882","article-title":"Communication: Probing Non-Equilibrium\nVibrational Relaxation Pathways of Highly Excited C\u2261N Stretching\nModes Following Ultrafast Back-Electron Transfer","volume":"136","author":"Lynch","year":"2012","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit67","doi-asserted-by":"publisher","first-page":"1286","DOI":"10.1021\/acs.jpclett.5b00356","article-title":"Measuring Coherently\nCoupled Intramolecular Vibrational and Charge-Transfer Dynamics with\nTwo-Dimensional Vibrational-Electronic Spectroscopy","volume":"6","author":"Courtney","year":"2015","journal-title":"J. Phys. Chem. Lett."},{"key":"2026102207420281000_cit68","doi-asserted-by":"publisher","first-page":"1558","DOI":"10.1021\/acs.jpclett.9b03752","article-title":"Determining the Orientation\nand Vibronic\nCouplings between Electronic and Vibrational Coordinates with Polarization-Selective\nTwo-Dimensional Vibrational-Electronic Spectroscopy","volume":"11","author":"Fox","year":"2020","journal-title":"J. Phys. Chem. Lett."},{"key":"2026102207420281000_cit69","doi-asserted-by":"publisher","first-page":"084505","DOI":"10.1063\/1.4866294","article-title":"Investigating\nvibrational anharmonic\ncouplings in cyanide-bridged transition metal mixed valence complexes\nusing two-dimensional infrared spectroscopy","volume":"140","author":"Slenkamp","year":"2014","journal-title":"J. Chem. Phys."},{"key":"2026102207420281000_cit70","doi-asserted-by":"publisher","first-page":"023609","DOI":"10.1063\/1.4943766","article-title":"Investigating Vibrational\nRelaxation in Cyanide-Bridged\nTransition Metal Mixed-Valence Complexes Using Two-Dimensional Infrared\nand Infrared Pump-Probe Spectroscopies","volume":"3","author":"Slenkamp","year":"2016","journal-title":"Struct.\nDyn."},{"key":"2026102207420281000_cit71","doi-asserted-by":"publisher","first-page":"11683","DOI":"10.1021\/jp073974n","article-title":"An Evaluation of Harmonic Vibrational\nFrequency Scale Factors","volume":"111","author":"Merrick","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit72","doi-asserted-by":"crossref","first-page":"391","DOI":"10.1002\/9780470166093.ch7","volume-title":"Prog. Inorg. Chem.","author":"Hush","year":"1967"},{"key":"2026102207420281000_cit73","doi-asserted-by":"publisher","first-page":"2270","DOI":"10.1021\/cr050010o","article-title":"Intervalence\nCharge Transfer (IVCT) in Trinuclear and\nTetranuclear Complexes of Iron, Ruthenium, and Osmium","volume":"106","author":"D\u2019Alessandro","year":"2006","journal-title":"Chem. Rev."},{"key":"2026102207420281000_cit74","doi-asserted-by":"publisher","first-page":"15637","DOI":"10.1021\/jp9613551","article-title":"Electroabsorption Studies of Intervalence\nCharge Transfer in (NC)5FeCNOs(NH3)5\u2013: Experimental Assessment of Charge-Transfer Distance,\nSolvent Reorganization, and Electronic Coupling Parameters","volume":"100","author":"Karki","year":"1996","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit75","doi-asserted-by":"publisher","first-page":"8320","DOI":"10.1021\/jp981352j","article-title":"Aspects\nof Intervalence Charge Transfer in Cyanide-Bridged Systems: Modulated\nElectric Field Assessment of Distances, Polarizability Changes, and\nAnticipated First Hyperpolarizability Characteristics","volume":"102","author":"Vance","year":"1998","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit76","doi-asserted-by":"publisher","first-page":"313","DOI":"10.1016\/S0301-0104(99)00400-0","article-title":"Comparative Absorption,\nElectroabsorption and Electrochemical Studies of Intervalence Electron\nTransfer and Electronic Coupling in Cyanide-Bridged Bimetallic Systems:\nAncillary Ligand Effects","volume":"253","author":"Vance","year":"2000","journal-title":"Chem. Phys."},{"key":"2026102207420281000_cit77","doi-asserted-by":"publisher","first-page":"1781","DOI":"10.1021\/cr0206667","article-title":"Ultrafast X-ray Absorption\nSpectroscopy","volume":"104","author":"Bressler","year":"2004","journal-title":"Chem. Rev."},{"key":"2026102207420281000_cit78","doi-asserted-by":"publisher","first-page":"221","DOI":"10.1146\/annurev.physchem.56.092503.141310","article-title":"Probing\nTransient Molecular Structures in Photochemical Processes Using Laser-Initiated\nTime-Resolved X-ray Absorption Spectroscopy","volume":"56","author":"Chen","year":"2005","journal-title":"Annu. Rev. Phys. Chem."},{"key":"2026102207420281000_cit79","doi-asserted-by":"publisher","first-page":"801","DOI":"10.1021\/ar500358q","article-title":"Ultrafast\nPhotophysics of Transition Metal Complexes","volume":"48","author":"Chergui","year":"2015","journal-title":"Acc. Chem. Res."},{"key":"2026102207420281000_cit80","doi-asserted-by":"publisher","first-page":"8010","DOI":"10.1039\/D1SC01864G","article-title":"Capturing\nPhotochemical and Photophysical Transformations in Iron Complexes\nwith Ultrafast X-ray Spectroscopy and Scattering","volume":"12","author":"Gaffney","year":"2021","journal-title":"Chem. Sci."},{"key":"2026102207420281000_cit81","doi-asserted-by":"publisher","first-page":"31","DOI":"10.1016\/j.ccr.2004.03.018","article-title":"Multiplet\nEffects in X-ray Spectroscopy","volume":"249","author":"Groot","year":"2005","journal-title":"Coord. Chem.\nRev."},{"key":"2026102207420281000_cit82","doi-asserted-by":"publisher","first-page":"3713","DOI":"10.1039\/D0SC06227H","article-title":"Revealing\nthe Bonding of Solvated Ru Complexes with Valence-to-Core Resonant\nInelastic X-ray Scattering","volume":"12","author":"Biasin","year":"2021","journal-title":"Chem. Sci."},{"key":"2026102207420281000_cit83","doi-asserted-by":"publisher","first-page":"1306","DOI":"10.1021\/acs.accounts.0c00171","article-title":"Density\nFunctional Theory Based Methods for the Calculation of X-ray Spectroscopy","volume":"53","author":"Besley","year":"2020","journal-title":"Acc. Chem. Res."},{"key":"2026102207420281000_cit84","doi-asserted-by":"publisher","first-page":"9411","DOI":"10.1021\/jp5055588","article-title":"X-ray Spectroscopic\nStudy of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions","volume":"118","author":"Penfold","year":"2014","journal-title":"J. Phys. Chem. A"},{"key":"2026102207420281000_cit85","doi-asserted-by":"publisher","first-page":"52","DOI":"10.1016\/j.ccr.2018.05.021","article-title":"Ultrafast\nPhotophysics and Photochemistry of Iron Hexacyanides in Solution:\nInfrared to X-ray Spectroscopic Studies","volume":"372","author":"Chergui","year":"2018","journal-title":"Coord.\nChem. Rev."},{"key":"2026102207420281000_cit86","doi-asserted-by":"publisher","first-page":"9904","DOI":"10.1021\/acs.inorgchem.3c00919","article-title":"Uncovering\nthe 3d and 4d Electronic Interactions in Solvated Ru Complexes with\n2p3d Resonant Inelastic X-ray Scattering","volume":"62","author":"Poulter","year":"2023","journal-title":"Inorg.\nChem."},{"key":"2026102207420281000_cit87","doi-asserted-by":"publisher","first-page":"4569","DOI":"10.1021\/jacs.0c11193","article-title":"Effect of 3d\/4p Mixing on 1s2p Resonant Inelastic X-ray\nScattering: Electronic Structure of Oxo-Bridged Iron Dimers","volume":"143","author":"Kroll","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026102207420281000_cit88","doi-asserted-by":"publisher","first-page":"17121","DOI":"10.1021\/ja408072q","article-title":"Metal-Ligand Covalency of Iron Complexes from High-Resolution\nResonant Inelastic X-ray Scattering","volume":"135","author":"Lundberg","year":"2013","journal-title":"J. Am.\nChem. Soc."},{"key":"2026102207420281000_cit89","doi-asserted-by":"publisher","first-page":"65","DOI":"10.1016\/j.ccr.2004.04.011","article-title":"High resolution\n1s core hole X-ray spectroscopy in 3d transition metal complexeselectronic\nand structural information","volume":"249","author":"Glatzel","year":"2005","journal-title":"Coord. Chem. Rev."}],"container-title":["The Journal of Physical\nChemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.6c03779","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/42\/11211\/68787759\/acs.jpcb.6c03779.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/42\/11211\/68787759\/acs.jpcb.6c03779.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T12:10:06Z","timestamp":1792671006000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/130\/42\/11211\/5447004\/Comprehensive-Experimental-and-Computational"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,8]]},"references-count":89,"journal-issue":{"issue":"42","published-online":{"date-parts":[[2026,10,8]]},"published-print":{"date-parts":[[2026,10,22]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.6c03779","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,8]]}}}