Photophysics & Electron Transport

Motivated by growing demand for renewable energy alternatives, interest in light-driven reactions will continue to increase. Even with advances in time-resolved optical and X-ray spectroscopy, which have led to greater understanding of photoinduced electron transfer on picosecond and femtosecond time-scales, many intermediates of photochemical reactions are still hard to capture experimentally. Computational approaches allow us to probe the geometric and electronic structure of molecules in multiple excited states, providing structures needed to detangle complex experimental spectra. 

Our goal is to predict photochemical properties accurately and efficiently. We study a wide range of photoactive materials from organic devices to metal-centered chromophores. 

Photoisomerization

Relevant References

Pinning Down Small Populations of Photoinduced Intermediates Using Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory Difference Spectra to Provide Mechanistic Insight into Controlling Pyridine Azo Dynamics with Protons. J. Phys. Chem. Lett., 2024, DOI: 10.1021/acs.jpclett.4c02155

Controlling Excited-State Dynamics via Protonation of Naphthalene-Based Azo Dyes. PhysChemChemPhys, 2024 DOI: 10.1039/D4CP00242C

Acid Violet 3: A Base Activated Water-Soluble Photoswitch. J. Phys. Chem. A, 2024, DOI: 10.1021/acs.jpca.3c07128

The Doorstop Proton: Acid-controlled Photoisomerization in Pyridine-Based Azo Dyes. New J. Chem., 2023, DOI: 10.1039/D3NJ01769A

Ultra-fast excited-state dynamics of substituted trans-naphthalene azo moieties. PhysChemChemPhys, 2023, DOI: 10.1039/D3CP01211E

Photocatalysis

Relevant References

PCET:

Proton-controlled Non-exponential Photoluminescence in a Pyridyl-Amidine-substituted Re(I) complex. Dalton Transactions, 2021 DOI: 10.1039/D1DT01132D

Computational Characterization of Competing Energy and Electron Transfer States in Bimetallic Donor-Acceptor Systems for Photocatalytic Conversion. J. Chem. Phys., 2016 DOI: 10.1063/1.4962254

Theoretical study of photoinduced charge separation in hetero-bimetallic Ru(II)-Co(III) complexes. J. Phys. Chem. B 2015 DOI: 10.1021/jp510950u

HAT:

Photoredox Product Selectivity Controlled by Persistent Radical Stability. J. Org. Chem. 2023 DOI: 10.1021/acs.joc.3c00490

Enhanced basicity of an electron donor–acceptor complex. Chem. Comm., 2023. DOI: 10.1039/d2cc05985a

Insights into the Mechanism of an Allylic Arylation Reaction via Photoredox Coupled Hydrogen Atom Transfer. J. Org. Chem., 2021 DOI: 10.1021/acs.joc.1c02235

Electron Transport

Relevant References

Finite Displacement Boltzmann Transport Theory Reveals the Detrimental Effects of High Frequency Phonons on Mobility. Phys. Rev. B, 2024 DOI: 10.1103/PhysRevB.109.094307

Efficiently Predicting Anisotropic Charge Carrier Mobilities in Organic Materials with the Boltzmann Transport Equation. J. Chem. Phys., 2023, DOI: 10.1063/5.0128125

Real Temperature Model of Dynamic Disorder in Molecular Crystals. J. Phys. Chem. A, 2022 DOI: 10.1021/acs.jpca.2c02120 with cover DOI: jpcafh/126/20

Investigation of transient localization in organic transistors: correlating anisotropic mobility and normal modes. Comm. Physics, 2019 DOI: 10.1038/s42005-019-0129-5

Photoexcitation

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy. Angew. Chem. Int. Ed., 2019, 58, 2-11. DOI: 10.1002/anie.201908065

Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes. J. Phys. Chem. A, 2019, DOI: 10.1021/acs.jpca.9b02927 

Molecular and Interfacial Calculations of Fe(II) Light Harvesters.  ChemSusChem, 2016  DOI: 10.1002/cssc.201600689

Exceptional Excited-State Lifetime of an Iron(II)–N-Heterocyclic Carbene Complex Explained. J. Phys. Chem. Lett. 2014 DOI: 10.1021/jz500829w

Iron sensitizer converts light to electrons with 92 % yield. Nature Chem., 2015 DOI: 10.1038/nchem.2365

A low-spin Fe(III) complex with 100 ps ligand-to-metal charge transfer photoluminescence. Nature, 2017  DOI: 10.1016/j.cplett.2017.03.085

Manipulating Charge Transfer Excited State Relaxation and Spin Crossover in Iron Coordination Complexes with Ligand Substitution. Chem. Sci., 2017 DOI: 10.1016/j.cplett.2017.03.085

A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II). Chem. Eur. J. 2014 DOI: 10.1002/chem.201405184

Ruthenium Complexes:

Excited State Dynamics of Bistridentate and Trisbidentate RuII Complexes of Quinoline-Pyrazole Ligands. Inorg. Chem., 2019, 58, 16354-16363. DOI: 10.1021/acs.inorgchem.9b01543

Influence of Triplet Surface Properties on Excited-State Deactivation of Expanded Cage Bis(tridentate)Ruthenium(II) Complexes. J. Phys. Chem. A, 2019, 255, 293-5299.  DOI: 0.1021/acs.jpca.9b02927

Chemical Consequences of Pyrazole Orientation in RuII Complexes of Unsymmetric Quinoline-Pyrazole Ligands. Dalton Trans., 2016 DOI: 10.1016/j.cplett.2017.03.085

Diastereomerization Dynamics of a Polyheteroaromatic Ru(II) complex. Inorg. Chem. 2016 DOI: 10.1021/acs.inorgchem.5b02893

A Homoleptic Trisbidentate Ru(II)-complex of a Novel Bidentate Biheteroaromatic Ligand based on Quinoline and Pyrazole groups: Structural, Electrochemical, Photophysical and Computational Characterization. Inorg. Chem. 2014 DOI: 10.1021/ic502432c

Tuning the Electronics of Bis(tridentate)ruthenium(II) Complexes with Long-Lived Excited States: Modifications to the Ligand Skeleton beyond Classical Electron Donor or Electron Withdrawing Group Decorations. Inorg. Chem. 2013 DOI: 10.1021/ic400009m