Exploring Ligand-to-Metal Charge-Transfer States in the Photo-Ferrioxalate System Using Excited-State Specific Optimization

Tran, Lan Nguyen; Neuscamman, Eric

doi:10.1021/acs.jpclett.3c01308

Title: Exploring Ligand-to-Metal Charge-Transfer States in the Photo-Ferrioxalate System Using Excited-State Specific Optimization

Journal Article · 13 August 2023 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.3c01308 · OSTI ID:2522071

^[1];

^[2]

International University, Ho Chi Minh City (Vietnam); Vietnam National University, Ho Chi Minh City (Vietnam)
University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

The photo-ferrioxalate system (PFS), [Fe(III)(C₂O₄)]^3–, more than an exact chemical actinometer, has been extensively applied in wastewater and environment treatment. Despite many experimental efforts to improve clarity, important aspects of the mechanism of ferrioxalate photolysis are still under debate. In this paper, we employ the recently developed WΓ-CASSCF to investigate the ligand-to-metal charge-transfer states that are key to ferrioxalate photolysis. This investigation provides a qualitative picture of these states and key potential energy surface features related to the photolysis. Furthermore, our theoretical results are consistent with the prompt charge-transfer picture seen in recent experiments and clarify some features that are not visible in experiments. Two ligand-to-metal charge-transfer states contribute to the photolysis of ferrioxalate, and the avoided crossing barrier between them is low compared with the initial photoexcitation energy. Our data also clarify that one Fe–O bond cleaves first, followed by the C–C bond and the other Fe–O bond.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017869

OSTI ID:: 2522071

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 33 Vol. 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Charge-Transfer Excitations: A Challenge for Time-Dependent Density Functional Theory That Has Been Met Kümmel, Stephan Advanced Energy Materials, Vol. 7, Issue 16 https://doi.org/10.1002/aenm.201700440	journal	May 2017
An Iron Complex with a Bent, O-Coordinated CO ₂ Ligand Discovered by Femtosecond Mid-Infrared Spectroscopy Straub, Steffen; Brünker, Paul; Lindner, Jörg Angewandte Chemie, Vol. 130, Issue 18 https://doi.org/10.1002/ange.201800672	journal	March 2018
Application Limits of the Ferrioxalate Actinometer** Wriedt, Benjamin; Ziegenbalg, Dirk ChemPhotoChem, Vol. 5, Issue 10 https://doi.org/10.1002/cptc.202100122	journal	August 2021
P y SCF: the Python-based simulations of chemistry framework : The PySCF program Sun, Qiming; Berkelbach, Timothy C.; Blunt, Nick S. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1340	journal	September 2017
Software update: The ORCA program system—Version 5.0 Neese, Frank WIREs Computational Molecular Science, Vol. 12, Issue 5 https://doi.org/10.1002/wcms.1606	journal	March 2022
Molpro: a general-purpose quantum chemistry program package: Molpro Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82	journal	July 2011
Metal-to-metal charge-transfer transitions: reliable excitation energies from ab initio calculations Domingo, Alex; Carvajal, Maria Àngels; de Graaf, Coen Theoretical Chemistry Accounts, Vol. 131, Issue 9 https://doi.org/10.1007/s00214-012-1264-1	journal	August 2012
Common pitfalls in chemical actinometry Wriedt, Benjamin; Ziegenbalg, Dirk Journal of Flow Chemistry, Vol. 10, Issue 1 https://doi.org/10.1007/s41981-019-00072-7	journal	February 2020
A chronological review of photochemical reactions of ferrioxalate at the molecular level: New insights into an old story Li, Xiaodie; Hou, Meiru; Fu, Yu Chinese Chemical Letters, Vol. 34, Issue 5 https://doi.org/10.1016/j.cclet.2022.107752	journal	May 2023
Mineralization of pentachlorophenol by ferrioxalate-assisted solar photo-Fenton process at mild pH Ye, Zhihong; Sirés, Ignasi; Zhang, Hui Chemosphere, Vol. 217 https://doi.org/10.1016/j.chemosphere.2018.10.221	journal	February 2019
Electron transfer and dissociation mechanism of ferrioxalate: A time resolved optical and EXAFS study Chen, Jie; Zhang, Hua; Tomov, Ivan V. Chemical Physics Letters, Vol. 437, Issue 1-3 https://doi.org/10.1016/j.cplett.2007.02.005	journal	March 2007
Statistical optimization of the photo-Fenton operational parameters with in situ ferrioxalate induction in the treatment of textile effluent Trigueros, Daniela Estelita Goes; Módenes, Aparecido Nivaldo; de Souza, Patrícia Simões Carraro Journal of Photochemistry and Photobiology A: Chemistry, Vol. 385 https://doi.org/10.1016/j.jphotochem.2019.112095	journal	December 2019
Initial Maximum Overlap Method for Large Systems by the Quantum Mechanics/Extremely Localized Molecular Orbital Embedding Technique Macetti, Giovanni; Genoni, Alessandro Journal of Chemical Theory and Computation, Vol. 17, Issue 7 https://doi.org/10.1021/acs.jctc.1c00388	journal	July 2021
Tracking Excited States in Wave Function Optimization Using Density Matrices and Variational Principles Tran, Lan Nguyen; Shea, Jacqueline A. R.; Neuscamman, Eric Journal of Chemical Theory and Computation, Vol. 15, Issue 9 https://doi.org/10.1021/acs.jctc.9b00351	journal	August 2019
Improving Excited-State Potential Energy Surfaces via Optimal Orbital Shapes Tran, Lan Nguyen; Neuscamman, Eric The Journal of Physical Chemistry A, Vol. 124, Issue 40 https://doi.org/10.1021/acs.jpca.0c07593	journal	September 2020
Excited State Specific Multi-Slater Jastrow Wave Functions Pineda Flores, Sergio D.; Neuscamman, Eric The Journal of Physical Chemistry A, Vol. 123, Issue 8 https://doi.org/10.1021/acs.jpca.8b10671	journal	January 2019
Ultrafast Time-Resolved X-ray Absorption Spectroscopy of Ferrioxalate Photolysis with a Laser Plasma X-ray Source and Microcalorimeter Array O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il The Journal of Physical Chemistry Letters, Vol. 8, Issue 5 https://doi.org/10.1021/acs.jpclett.7b00078	journal	February 2017
Practical Ferrioxalate Actinometry for the Determination of Photon Fluxes in Production-Oriented Photoflow Reactors Vandekerckhove, Bavo; Piens, Nicola; Metten, Bert Organic Process Research & Development, Vol. 26, Issue 8 https://doi.org/10.1021/acs.oprd.2c00079	journal	June 2022
Mechanism of Ferric Oxalate Photolysis Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr ACS Earth and Space Chemistry, Vol. 1, Issue 5 https://doi.org/10.1021/acsearthspacechem.7b00026	journal	June 2017
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin Chemical Reviews, Vol. 105, Issue 11 https://doi.org/10.1021/cr0505627	journal	November 2005
Electron Transfer Mechanism and Photochemistry of Ferrioxalate Induced by Excitation in the Charge Transfer Band Chen, Jie; Zhang, Hua; Tomov, Ivan V. Inorganic Chemistry, Vol. 47, Issue 6 https://doi.org/10.1021/ic7016566	journal	February 2008
Self-Consistent Field Calculations of Excited States Using the Maximum Overlap Method (MOM) ^† Gilbert, Andrew T. B.; Besley, Nicholas A.; Gill, Peter M. W. The Journal of Physical Chemistry A, Vol. 112, Issue 50 https://doi.org/10.1021/jp801738f	journal	December 2008
New Insight into Photochemistry of Ferrioxalate Pozdnyakov, Ivan P.; Kel, Oksana V.; Plyusnin, Victor F. The Journal of Physical Chemistry A, Vol. 112, Issue 36 https://doi.org/10.1021/jp8040583	journal	September 2008
Comment on “New Insight into Photochemistry of Ferrioxalate” Chen, Jie; Dvornikov, Alexander S.; Rentzepis, Peter M. The Journal of Physical Chemistry A, Vol. 113, Issue 30 https://doi.org/10.1021/jp809535q	journal	July 2009
Reply to “Comment on ‘New insight into Photochemistry of Ferrioxalate’” Pozdnyakov, Ivan P.; Kel, Oksana V.; Plyusnin, Victor F. The Journal of Physical Chemistry A, Vol. 113, Issue 30 https://doi.org/10.1021/jp810301g	journal	July 2009
Femtosecond infrared spectroscopy reveals the primary events of the ferrioxalate actinometer Straub, Steffen; Brünker, Paul; Lindner, Jörg Physical Chemistry Chemical Physics, Vol. 20, Issue 33 https://doi.org/10.1039/C8CP03824D	journal	January 2018
Time-resolved Fourier-transform infrared spectroscopy reveals the hidden bimolecular process of the ferrioxalate actinometer Pilz, Frank Hendrik; Lindner, Jörg; Vöhringer, Peter Physical Chemistry Chemical Physics, Vol. 21, Issue 43 https://doi.org/10.1039/C9CP05233J	journal	January 2019
Ultrafast photoelectron spectroscopy of photoexcited aqueous ferrioxalate Longetti, L.; Barillot, T. R.; Puppin, M. Physical Chemistry Chemical Physics, Vol. 23, Issue 44 https://doi.org/10.1039/D1CP02872C	journal	January 2021
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Quantum Yield of the Ferrioxalate Actinometer Lee, John; Seliger, H. H. The Journal of Chemical Physics, Vol. 40, Issue 2 https://doi.org/10.1063/1.1725147	journal	January 1964
On the relation between time-dependent and variational density functional theory approaches for the determination of excitation energies and transition moments. Ziegler, Tom; Seth, Michael; Krykunov, Mykhaylo The Journal of Chemical Physics, Vol. 130, Issue 15 https://doi.org/10.1063/1.3114988	journal	April 2009
Ultraviolet photochemical reaction of [Fe(III)(C2O4)3]3− in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser Ogi, Y.; Obara, Y.; Katayama, T. Structural Dynamics, Vol. 2, Issue 3 https://doi.org/10.1063/1.4918803	journal	April 2015
Geometry optimization made simple with translation and rotation coordinates Wang, Lee-Ping; Song, Chenchen The Journal of Chemical Physics, Vol. 144, Issue 21 https://doi.org/10.1063/1.4952956	journal	June 2016
On the relation between adiabatic time dependent density functional theory (TDDFT) and the ΔSCF-DFT method. Introducing a numerically stable ΔSCF-DFT scheme for local functionals based on constricted variational DFT Park, Young Choon; Krykunov, Mykhaylo; Ziegler, Tom Molecular Physics, Vol. 113, Issue 13-14 https://doi.org/10.1080/00268976.2014.1003260	journal	January 2015
Practical Chemical Actinometry—A Review Rabani, Joseph; Mamane, Hadas; Pousty, Dana Photochemistry and Photobiology, Vol. 97, Issue 5 https://doi.org/10.1111/php.13429	journal	July 2021

Similar Records

Low temperature synthesis of bismuth ferrite nanoparticles by a ferrioxalate precursor method

Journal Article · 2005 · Materials Research Bulletin · OSTI ID:20889808

Ghosh, Sushmita; Dasgupta, Subrata; Sen, Amarnath; +1 more

Determination of valence states in Fe/sub 3/O/sub 4/ by resonant photoemission

Journal Article · 1989 · J. Vac. Sci. Technol., A; (United States) · OSTI ID:6182521

Lad, R J; Henrich, V E

Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

Journal Article · 2017 · Journal of Physical Chemistry Letters · OSTI ID:1344424

O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il; +16 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Energy
Ligand to metal charge transfer
Mathematical methods
Photodissociation
Time dependant density functional theory

Title: Exploring Ligand-to-Metal Charge-Transfer States in the Photo-Ferrioxalate System Using Excited-State Specific Optimization

Citation Formats

References (35)

Similar Records

Related Subjects