An Ab Initio Correction Vector Restricted Active Space Approach to the L-Edge XAS and 2p3d RIXS Spectra of Transition Metal Complexes

Lee, Seunghoon; Zhai, Huanchen; Chan, Garnet Kin-Lic

doi:10.1021/acs.jctc.3c00663

Title: An Ab Initio Correction Vector Restricted Active Space Approach to the L-Edge XAS and 2p3d RIXS Spectra of Transition Metal Complexes

Journal Article · Thu Oct 19 00:00:00 EDT 2023 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.3c00663· OSTI ID:2203001

^[1];

^[2]; Chan, Garnet Kin-Lic ^[2]

Department of Chemistry, Seoul National University, Seoul 151-747, South Korea, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States

We describe an ab initio approach to simulate Ledge X-ray absorption (XAS) and 2p3d resonant inelastic X-ray scattering (RIXS) spectroscopies. We model the strongly correlated electronic structure within a restricted active space and employ a correction vector formulation instead of sum-overstate expressions for the spectra, thus eliminating the need to calculate a large number of intermediate and final electronic states. We present benchmark simulations of the XAS and RIXS spectra of the iron complexes [FeCl₄]^1–/2– and [Fe(SCH₃)₄]^1–/2– and interpret the spectra by deconvolving the correction vectors. Our approach represents a step toward simulating the X-ray spectroscopies of larger metal cluster systems that play a pivotal role in biology.

View Journal Article

Cite

Export

Save

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

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

Grant/Contract Number:: SC0023318; SC0019374

OSTI ID:: 2203001

Alternate ID(s):: OSTI ID: 2208750

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Vol. 19 Journal Issue: 21; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (25)

An algorithm for large scale density matrix renormalization group calculations Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 120, Issue 7 https://doi.org/10.1063/1.1638734	journal	February 2004
New Relativistic ANO Basis Sets for Transition Metal Atoms Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke The Journal of Physical Chemistry A, Vol. 109, Issue 29 https://doi.org/10.1021/jp0581126	journal	July 2005
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
Electronic Spectra of Iron–Sulfur Complexes Measured by 2p3d RIXS Spectroscopy Van Kuiken, Benjamin E.; Hahn, Anselm W.; Nayyar, Brahamjot Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b01010	journal	May 2018
Comparison of multireference *ab initio* wavefunction methodologies for X-ray absorption edges: A case study on [Fe(II/III)Cl ₄ ] ^2–/1– molecules Maganas, Dimitrios; Kowalska, Joanna K.; Nooijen, Marcel The Journal of Chemical Physics, Vol. 150, Issue 10 https://doi.org/10.1063/1.5051613	journal	March 2019
Highly correlated calculations with a polynomial cost algorithm: A study of the density matrix renormalization group Chan, Garnet Kin-Lic; Head-Gordon, Martin The Journal of Chemical Physics, Vol. 116, Issue 11 https://doi.org/10.1063/1.1449459	journal	March 2002
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Single-crystal spectroscopic studies of Fe(SR)42- (R = 2-(Ph)C6H4): electronic structure of the ferrous site in rubredoxin Gebhard, Matthew S.; Koch, Stephen A.; Millar, Michelle Journal of the American Chemical Society, Vol. 113, Issue 5 https://doi.org/10.1021/ja00005a030	journal	February 1991
A comparison between the one- and two-step spin–orbit coupling approaches based on the ab initio density matrix renormalization group Zhai, Huanchen; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 157, Issue 16 https://doi.org/10.1063/5.0107805	journal	October 2022
Iron L _2,3 -Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase Kowalska, Joanna K.; Nayyar, Brahamjot; Rees, Julian A. Inorganic Chemistry, Vol. 56, Issue 14 https://doi.org/10.1021/acs.inorgchem.7b00852	journal	June 2017
Density-functional approximation for the correlation energy of the inhomogeneous electron gas Perdew, John P. Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8822	journal	June 1986
A combined DFT and restricted open-shell configuration interaction method including spin-orbit coupling: Application to transition metal L-edge X-ray absorption spectroscopy Roemelt, Michael; Maganas, Dimitrios; DeBeer, Serena The Journal of Chemical Physics, Vol. 138, Issue 20 https://doi.org/10.1063/1.4804607	journal	May 2013
Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes Josefsson, Ida; Kunnus, Kristjan; Schreck, Simon The Journal of Physical Chemistry Letters, Vol. 3, Issue 23 https://doi.org/10.1021/jz301479j	journal	November 2012
Determinant based configuration interaction algorithms for complete and restricted configuration interaction spaces Olsen, Jeppe; Roos, Björn O.; Jo/rgensen, Poul The Journal of Chemical Physics, Vol. 89, Issue 4 https://doi.org/10.1063/1.455063	journal	August 1988
Efficient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations Neese, Frank The Journal of Chemical Physics, Vol. 122, Issue 3 https://doi.org/10.1063/1.1829047	journal	January 2005
Quantum Theory of Many-Particle Systems. III. Extension of the Hartree-Fock Scheme to Include Degenerate Systems and Correlation Effects Löwdin, Per-Olov Physical Review, Vol. 97, Issue 6 https://doi.org/10.1103/PhysRev.97.1509	journal	March 1955
Libcint: An efficient general integral library for Gaussian basis functions Sun, Qiming Journal of Computational Chemistry, Vol. 36, Issue 22 https://doi.org/10.1002/jcc.23981	journal	June 2015
Low communication high performance ab initio density matrix renormalization group algorithms Zhai, Huanchen; Chan, Garnet Kin-Lic The Journal of Chemical Physics, Vol. 154, Issue 22 https://doi.org/10.1063/5.0050902	journal	June 2021
L-edge X-ray Absorption Spectroscopy of Non-Heme Iron Sites: Experimental Determination of Differential Orbital Covalency Wasinger, Erik C.; de Groot, Frank M. F.; Hedman, Britt Journal of the American Chemical Society, Vol. 125, Issue 42 https://doi.org/10.1021/ja034634s	journal	October 2003
Valence bond approach to exact nonlinear optical properties of conjugated systems Soos, Z. G.; Ramasesha, S. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456160	journal	January 1989
Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model Chilkuri, Vijay Gopal; DeBeer, Serena; Neese, Frank Inorganic Chemistry, Vol. 56, Issue 17 https://doi.org/10.1021/acs.inorgchem.7b01371	journal	August 2017
Orbital Optimized Density Functional Theory for Electronic Excited States Hait, Diptarka; Head-Gordon, Martin The Journal of Physical Chemistry Letters, Vol. 12, Issue 19 https://doi.org/10.1021/acs.jpclett.1c00744	journal	May 2021
Electronic landscape of the P-cluster of nitrogenase as revealed through many-electron quantum wavefunction simulations Li, Zhendong; Guo, Sheng; Sun, Qiming Nature Chemistry, Vol. 11, Issue 11 https://doi.org/10.1038/s41557-019-0337-3	journal	September 2019
Time-Step Targeting Time-Dependent and Dynamical Density Matrix Renormalization Group Algorithms with ab Initio Hamiltonians Ronca, Enrico; Li, Zhendong; Jimenez-Hoyos, Carlos A. Journal of Chemical Theory and Computation, Vol. 13, Issue 11 https://doi.org/10.1021/acs.jctc.7b00682	journal	October 2017
Recent developments in the P y SCF program package Sun, Qiming; Zhang, Xing; Banerjee, Samragni The Journal of Chemical Physics, Vol. 153, Issue 2 https://doi.org/10.1063/5.0006074	journal	July 2020

Similar Records

K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites

Journal Article · Thu Feb 09 00:00:00 EST 2017 · Coordination Chemistry Reviews · OSTI ID:2203001

Baker, Michael L.; Mara, Michael W.; Yan, James J.; +3 more

Uncovering the 3d and 4d Electronic Interactions in Solvated Ru Complexes with 2p3d Resonant Inelastic X-ray Scattering

Journal Article · Wed Jun 14 00:00:00 EDT 2023 · Inorganic Chemistry · OSTI ID:2203001

Poulter, Benjamin I.; Biasin, Elisa; Nowak, Stanisław H.; +6 more

Enhanced 5f-δ bonding in [U(C ₇ H ₇ ) ₂ ] ⁻ : C K-edge XAS, magnetism, and ab initio calculations

Journal Article · Tue Sep 21 00:00:00 EDT 2021 · ChemComm · OSTI ID:2203001

Qiao, Yusen; Ganguly, Gaurab; Booth, Corwin H.; +10 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Energy
Ligands
Natural orbitals
Quantum mechanics

Title: An Ab Initio Correction Vector Restricted Active Space Approach to the L-Edge XAS and 2p3d RIXS Spectra of Transition Metal Complexes

Citation Formats

References (25)

Similar Records

Related Subjects