2024
Modeling Electrochemical Vacancy Regeneration in Single-Walled Carbon Nanotubes
Jelušić J, Menzel J, Bertrand Q, Crabtree R, Wang H, Brudvig G, Batista V. Modeling Electrochemical Vacancy Regeneration in Single-Walled Carbon Nanotubes. The Journal Of Physical Chemistry Letters 2024, 15: 7788-7792. PMID: 39048317, DOI: 10.1021/acs.jpclett.4c01293.Peer-Reviewed Original ResearchProton-coupled electron transferDensity functional theorySingle-walled carbon nanotubesC-H bondsQuantum mechanics/molecular mechanicsDiverse catalytic reactionsCarbene characterCarbon nanotubesC-HAdjacent carbonWater dissociationElectron transferCatalytic reactionsCatalytic intermediatesFunctional theoryHydrogen atomsKetone groupForce-fieldCarbon atomsHydroxyl groupsElectrochemical regenerationZigzag single-walled carbon nanotubesElectrochemical potentialKetonesVacancy defectsBenchmarking various nonadiabatic semiclassical mapping dynamics methods with tensor-train thermo-field dynamics
Liu Z, Lyu N, Hu Z, Zeng H, Batista V, Sun X. Benchmarking various nonadiabatic semiclassical mapping dynamics methods with tensor-train thermo-field dynamics. The Journal Of Chemical Physics 2024, 161: 024102. PMID: 38980091, DOI: 10.1063/5.0208708.Peer-Reviewed Original ResearchNonadiabatic dynamics methodsZero-point energy parameterOne-dimensional scattering modelLinear vibronic coupling modelEhrenfest mean-fieldSpin-boson modelThermo field dynamicsZero-temperature dynamicsAccurate quantum dynamics simulationsNumerically exact calculationsVibronic coupling modelFinite-temperature dynamicsZero-point energyDynamics methodStudy of electron transferNonadiabatic dynamicsQuasiclassical dynamicsNonadiabatic processesConical intersectionMean-fieldExact calculationsElectronic transitionsElectron transferCondensed phasePhotochemical reactionsWater Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II
Liu J, Yang K, Long Z, Armstrong W, Brudvig G, Batista V. Water Ligands Regulate the Redox Leveling Mechanism of the Oxygen-Evolving Complex of the Photosystem II. Journal Of The American Chemical Society 2024, 146: 15986-15999. PMID: 38833517, DOI: 10.1021/jacs.4c02926.Peer-Reviewed Original ResearchProton-coupled electron transferOxygen-evolving complexWater insertionWater ligandsCatalytic cycleMolecular dynamicsO-O bondQuantum mechanics/molecular mechanicsConformational changesFree energy changeLigand environmentElectron transferLigand exchangePhotosystem IIOxygen evolutionWater binding mechanismsEnergy changeLigandBinding mechanismAqueous environmentRedoxWater bindingLigand bindingCatalystIsomerization
2023
A quantitative assessment of (bacterio)chlorophyll assignments in the cryo-EM structure of the Chloracidobacterium thermophilum reaction center
Gisriel C, Flesher D, Long Z, Liu J, Wang J, Bryant D, Batista V, Brudvig G. A quantitative assessment of (bacterio)chlorophyll assignments in the cryo-EM structure of the Chloracidobacterium thermophilum reaction center. Photosynthesis Research 2023, 1-10. PMID: 37749456, DOI: 10.1007/s11120-023-01047-5.Peer-Reviewed Original ResearchCryo-EM mapsCryogenic electron microscopy structureReaction centersHydrogen bond donorCryo-EM structureElectron microscopy structureReaction center complexBond donorPhotosynthetic organismsMicroscopy structureProtein complexesElectron transferMolecular structureFunctional insightsStructural biologyLight harvestingProtein environmentChemical environmentExperimental cryo-EM mapsDownstream investigationsCenter complexPrimary pigmentEnergy transferStructural dataAcetyl moiety
2022
Microbial biofilms as living photoconductors due to ultrafast electron transfer in cytochrome OmcS nanowires
Neu J, Shipps CC, Guberman-Pfeffer MJ, Shen C, Srikanth V, Spies JA, Kirchhofer ND, Yalcin SE, Brudvig GW, Batista VS, Malvankar NS. Microbial biofilms as living photoconductors due to ultrafast electron transfer in cytochrome OmcS nanowires. Nature Communications 2022, 13: 5150. PMID: 36071037, PMCID: PMC9452534, DOI: 10.1038/s41467-022-32659-5.Peer-Reviewed Original ResearchConceptsUltrafast electron transferElectron transferPhotoconductive atomic force microscopyFemtosecond transient absorption spectroscopyQuantum dynamics simulationsMicrobial electron transferAtomic force microscopyTransient absorption spectroscopyValue-added chemicalsIndividual nanowiresWhole-cell catalysisPhotoconductive materialForce microscopyCarrier densityCatalytic performanceNanowiresAbsorption spectroscopyPhotoactive proteinsEfficient productionPhotoconductorsSynthetic photosensitizersDynamics simulationsGeobacter sulfurreducensBiodegradable materialsElectronic interfaceUltrafast Charge Relocation Dynamics in Enol–Keto Tautomerization Monitored with a Local Soft-X-ray Probe
Soley M, Videla P, Nibbering E, Batista V. Ultrafast Charge Relocation Dynamics in Enol–Keto Tautomerization Monitored with a Local Soft-X-ray Probe. The Journal Of Physical Chemistry Letters 2022, 13: 8254-8263. PMID: 36018775, PMCID: PMC9465716, DOI: 10.1021/acs.jpclett.2c02037.Peer-Reviewed Original ResearchConceptsSoft X-ray probeSoft X-ray spectroscopyFull quantum treatmentPump-probe spectroscopyUltrafast time scaleQuantum treatmentHydrogen fuel cellsNuclear dynamicsElectronic excitationEnol-keto tautomerizationPCET mechanismOxygen reductionInterplay of protonsFrontier orbitalsWater splittingCharge relocationElectron transferElectronic structure rearrangementLocal excitationTautomerization reactionImportant reactionsFuel cellsElementary stepsChemical reactionsH atoms
2021
Charge Stabilization in Axially Linked Donor – Aluminum(III) Porphyrin – Fullerene Reaction Center Models
Zarrabi N, Seetharaman S, Chaudhuri S, Holzer N, Batista V, van der Est A, D'Souza F, Poddutoori P. Charge Stabilization in Axially Linked Donor – Aluminum(III) Porphyrin – Fullerene Reaction Center Models. ECS Meeting Abstracts 2021, MA2021-01: 781-781. DOI: 10.1149/ma2021-0116781mtgabs.Peer-Reviewed Original ResearchCharge-separated stateFinal charge-separated stateReaction center modelsRedox potentialRadical pairSequential electron transferSubstitution of phenylCoordination bondsMeso positionsPentafluorophenyl groupsDonor unitsElectron transferCharge stabilizationPorphyrin planeTriad resultsC60Ground stateTrifluorophenylCovalentPorphyrinsRedoxPhenylBondsAcceptorDonorsTuning the Conduction Band for Interfacial Electron Transfer: Dye-Sensitized Sn x Ti1–x O2 Photoanodes for Water Splitting
Spies J, Swierk J, Kelly H, Capobianco M, Regan K, Batista V, Brudvig G, Schmuttenmaer C. Tuning the Conduction Band for Interfacial Electron Transfer: Dye-Sensitized Sn x Ti1–x O2 Photoanodes for Water Splitting. ACS Applied Energy Materials 2021, 4: 4695-4703. DOI: 10.1021/acsaem.1c00305.Peer-Reviewed Original ResearchDFT calculationsAbsorption spectroscopyInterfacial electron transfer dynamicsUltrafast transient absorption spectroscopyInterfacial electron transferElectron transfer dynamicsUltrafast electron injectionConduction bandPeriodic DFT calculationsTransient absorption spectroscopyLinear absorption spectroscopyDye sensitizersWater splittingElectron transferTransfer dynamicsComposition of SnElectron acceptorAbsorption spectraElectron injectionD characterElectronic statesSpectroscopyPhotoanodeSnDye
2019
Vibronic Effects in the Ultrafast Interfacial Electron Transfer of Perylene-Sensitized TiO2 Surfaces
Oliboni R, Yan H, Fan H, Abraham B, Avenoso J, Galoppini E, Batista V, Gundlach L, Rego L. Vibronic Effects in the Ultrafast Interfacial Electron Transfer of Perylene-Sensitized TiO2 Surfaces. The Journal Of Physical Chemistry C 2019, 123: 12599-12607. DOI: 10.1021/acs.jpcc.9b02106.Peer-Reviewed Original ResearchVibronic effectsAbsorption spectraNonadiabatic quantum dynamics simulationsOptical gap decreasesUltrafast transient absorption spectroscopyUltrafast interfacial electron transferQuantum dynamics simulationsEnergy modesTransient absorption spectroscopyTransient absorption spectraQuantum dynamicsBroadband spectroscopyElectron transferVelocity autocorrelation functionClassical trajectoriesExcited statesEnergy shiftGap decreasesWide-band limitS1 stateElectronic populationAbsorption spectroscopyInterfacial electron transferCondon approximationNonequilibrium modesEffect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO)3X
Martinez J, La Porte N, Chaudhuri S, Sinopoli A, Bae Y, Sohail M, Batista V, Wasielewski M. Effect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO)3X. The Journal Of Physical Chemistry C 2019, 123: 10178-10190. DOI: 10.1021/acs.jpcc.8b12264.Peer-Reviewed Original ResearchNaphthalenediimide radical anionElectron transfer rateElectronic couplingRadical anionX-ray structural studiesAppropriate reference moleculesReaction free energyPhotocatalytic CO2 reductionFree energy changeArtificial photosynthesisNDI chromophoresElectron transferMid-IR spectroscopyCatalyst resultsUV/Constitutional isomersPhotocatalytic reductionCO2 reductionReference moleculeStructural studiesFree energyEnergy changeFirst intermediateAnionsTransfer rate
2018
High-Energy Charge-Separated States by Reductive Electron Transfer Followed by Electron Shift in the Tetraphenylethylene–Aluminum(III) Porphyrin–Fullerene Triad
Zarrabi N, Agatemor C, Lim G, Matula A, Bayard B, Batista V, D’Souza F, Poddutoori P. High-Energy Charge-Separated States by Reductive Electron Transfer Followed by Electron Shift in the Tetraphenylethylene–Aluminum(III) Porphyrin–Fullerene Triad. The Journal Of Physical Chemistry C 2018, 123: 131-143. DOI: 10.1021/acs.jpcc.8b09500.Peer-Reviewed Original ResearchCharge-separated stateCharge separationTime-resolved spectroscopic techniquesReductive electron transferCharge separated statesExcited-state propertiesReference dyadsExcited singlet stateTetraphenylethylene unitsArtificial photosynthesisSupramolecular triadElectron transferSpectroscopic techniquesCovalent bondsPorphyrin planeTetraphenylethyleneElectron migrationPhotochemical reactionsChemical energyElectron shiftSinglet stateAlPorFullerenesPorphyrinsSeparationUltrafast proton-assisted tunneling through ZrO 2 in dye-sensitized SnO 2 -core/ZrO 2 -shell films
Swierk JR, McCool NS, Röhr JA, Hedström S, Konezny SJ, Nemes CT, Xu P, Batista VS, Mallouk TE, Schmuttenmaer CA. Ultrafast proton-assisted tunneling through ZrO 2 in dye-sensitized SnO 2 -core/ZrO 2 -shell films. Chemical Communications 2018, 54: 7971-7974. PMID: 29961797, DOI: 10.1039/c8cc04189j.Peer-Reviewed Original ResearchPhotoexcited radical anion super-reductants for solar fuels catalysis
La Porte N, Martinez J, Chaudhuri S, Hedström S, Batista V, Wasielewski M. Photoexcited radical anion super-reductants for solar fuels catalysis. Coordination Chemistry Reviews 2018, 361: 98-119. DOI: 10.1016/j.ccr.2018.01.018.Peer-Reviewed Original ResearchMetal centerCarbon-neutral energy economyCharge-separated lifetimeSolar fuel catalysisReduction of CO2Catalytic transformationsRadical anionFuel catalysisElectron transferImportant reactionsRedox potentialActive complexGlobal energy demandExcitation wavelengthSolar spectrumCarbon dioxideLargest possible portionReactionNsRylenediimidesCatalysisEnergy economyAnionsSolar energyChromophoreDirect Interfacial Electron Transfer from High-Potential Porphyrins into Semiconductor Surfaces: A Comparison of Linkers and Anchoring Groups
Jiang J, Spies J, Swierk J, Matula A, Regan K, Romano N, Brennan B, Crabtree R, Batista V, Schmuttenmaer C, Brudvig G. Direct Interfacial Electron Transfer from High-Potential Porphyrins into Semiconductor Surfaces: A Comparison of Linkers and Anchoring Groups. The Journal Of Physical Chemistry C 2018, 122: 13529-13539. DOI: 10.1021/acs.jpcc.7b12405.Peer-Reviewed Original ResearchMetal oxide surfacesDirect interfacial electron transferTime-resolved terahertzInterfacial electron transferOxide surfaceSemiconductor surfacesPhotoelectrochemical stabilitySnO2 substratePhotoelectrochemical cellsInjection yieldTransient spectroscopySurfaceAqueous photoelectrochemical cellDye photosensitizerIET dynamicsTerahertzElectron transferSeries of linkersDirect contactSpectroscopyAbsorption spectroscopyTransferTransient absorption spectroscopyOverall length
2017
Ultrafast photo-induced charge transfer of 1-naphthol and 2-naphthol to halocarbon solvents
Chaudhuri S, Rudshteyn B, Prémont-Schwarz M, Pines D, Pines E, Huppert D, Nibbering E, Batista V. Ultrafast photo-induced charge transfer of 1-naphthol and 2-naphthol to halocarbon solvents. Chemical Physics Letters 2017, 683: 49-56. DOI: 10.1016/j.cplett.2017.03.080.Peer-Reviewed Original ResearchHalocarbon solventsPhoto-induced charge transferFirst solvation shellQuantum chemistry computationsFemtosecond IR spectroscopyClose contact interactionsIR spectroscopyHalocarbon moleculesSolvation shellElectron transferChemistry computationsCharge transferFluorescence quenchingElectronic structureSolventDe-excitation mechanismNaphtholMoleculesTransferDecay rateQuenchingFaster decay rateInteractionShellStructureInterfacial Electron Transfer Followed by Photooxidation in N , N -Bis( p -anisole)aminopyridine–Aluminum(III) Porphyrin–Titanium(IV) Oxide Self-Assembled Photoanodes
Lim G, Hedström S, Jung K, Smith P, Batista V, D’Souza F, van der Est A, Poddutoori P. Interfacial Electron Transfer Followed by Photooxidation in N , N -Bis( p -anisole)aminopyridine–Aluminum(III) Porphyrin–Titanium(IV) Oxide Self-Assembled Photoanodes. The Journal Of Physical Chemistry C 2017, 121: 14484-14497. DOI: 10.1021/acs.jpcc.7b04197.Peer-Reviewed Original Research
2015
Isotopic Probe Illuminates the Role of the Electrode Surface in Proton Coupled Hydride Transfer Electrochemical Reduction of Pyridinium on Pt(111)
Zeitler E, Ertem M, Pander J, Yan Y, Batista V, Bocarsly A. Isotopic Probe Illuminates the Role of the Electrode Surface in Proton Coupled Hydride Transfer Electrochemical Reduction of Pyridinium on Pt(111). Journal Of The Electrochemical Society 2015, 162: h938-h944. DOI: 10.1149/2.0821514jes.Peer-Reviewed Original ResearchEquilibrium isotope effectPt surfacePyridinium reductionVoltammetric half-wave potentialElectrochemical CO2 reductionObserved redox potentialsOne-electron reductionHalf-wave potentialDeuterium substitutionPyridinium sitesElectrochemical reductionCyclic voltammogramsElectrode surfaceCathodic waveElectron transferPyridine solutionBrønsted acidsCO2 reductionRedox potentialIsotopic probesReaction mechanismPyridiniumIsotopic substitutionH atomsIsotope effectPhotoinduced Water Oxidation at the Aqueous GaN (101̅0) Interface: Deprotonation Kinetics of the First Proton-Coupled Electron-Transfer Step
Ertem M, Kharche N, Batista V, Hybertsen M, Tully J, Muckerman J. Photoinduced Water Oxidation at the Aqueous GaN (101̅0) Interface: Deprotonation Kinetics of the First Proton-Coupled Electron-Transfer Step. ACS Catalysis 2015, 5: 2317-2323. DOI: 10.1021/acscatal.5b00054.Peer-Reviewed Original ResearchWater oxidation mechanismElectron transfer stepWater oxidationProton transferFree energy changeElectron transferProton-coupled electron transfer stepsOxidation mechanismOverall water splitting reactionAb initio molecular dynamicsPhotoinduced water oxidationHydrogen bonding interactionsRadical ion intermediatesFirst solvation shellWater splitting reactionInitio molecular dynamicsPhotoelectrochemical water splittingCluster model approachPCET stepsProton reductionBonding interactionsSplitting reactionWater dissociationHydrogen bondingSolvation shellFacet-Dependent Photoelectrochemical Performance of TiO2 Nanostructures: An Experimental and Computational Study
Li C, Koenigsmann C, Ding W, Rudshteyn B, Yang KR, Regan KP, Konezny SJ, Batista VS, Brudvig GW, Schmuttenmaer CA, Kim JH. Facet-Dependent Photoelectrochemical Performance of TiO2 Nanostructures: An Experimental and Computational Study. Journal Of The American Chemical Society 2015, 137: 1520-1529. PMID: 25563343, DOI: 10.1021/ja5111078.Peer-Reviewed Original ResearchPhotoelectrochemical performanceInterfacial electron transferTimes higher photocatalytic activityElectron injection dynamicsMK-2 dyeStrong covalent interactionHigher photocatalytic activityOverall cell efficiencyElectron transferCovalent interactionsCrystalline nanoparticlesMethyl orangePhotocatalytic activityTime-resolved THz spectroscopyComputational studyCrystalline structureSurface areaNanoparticlesInjection dynamicsSurface atomsPhotochemical performanceDyeSurface energyMK-2Fundamental insightsInterfacial electron transfer in photoanodes based on phosphorus( v ) porphyrin sensitizers co-deposited on SnO 2 with the Ir(III)Cp* water oxidation precatalyst
Poddutoori P, Thomsen J, Milot R, Sheehan S, Negre C, Garapati V, Schmuttenmaer C, Batista V, Brudvig G, van der Est A. Interfacial electron transfer in photoanodes based on phosphorus( v ) porphyrin sensitizers co-deposited on SnO 2 with the Ir(III)Cp* water oxidation precatalyst. Journal Of Materials Chemistry A 2015, 3: 3868-3879. DOI: 10.1039/c4ta07018f.Peer-Reviewed Original ResearchInterfacial electron transferElectron paramagnetic resonanceQuantum dynamics simulationsElectron transferPhotoanode componentCatalytic water oxidationEfficient interfacial electron transferDynamics simulationsMetal oxide surfacesSolar cellsTime-resolved terahertz spectroscopy measurementsSteady-state fluorescenceTypes of porphyrinsTerahertz spectroscopy measurementsOxidation precatalystWater oxidationAxial coordinationChloride ligandsPorphyrin sensitizersOxidation stateCharge recombinationParamagnetic resonanceSnO 2Phosphorus porphyrinsSpectroscopy measurements