Triplet‐Singlet Emission of d‐Block Metal Complexes Characterized by Spin‐Orbit Natural Transition Orbitals

Zaichenko, A.; Autschbach, J.

doi:10.1002/open.202300291

Title: Triplet‐Singlet Emission of d‐Block Metal Complexes Characterized by Spin‐Orbit Natural Transition Orbitals

Journal Article · 04 March 2024 · ChemistryOpen

DOI: https://doi.org/10.1002/open.202300291 · OSTI ID:2318763

^[1];

^[1]

Department of Chemistry University at Buffalo State University of New York Buffalo NY 14260-3000 USA

Abstract Spin‐orbit natural transition orbital (SO‐NTO) methodology, recently developed in our group for complete and restricted active space (CAS/RAS) wavefunction calculations, is applied to analyze triplet‐to‐singlet emission in transition metal complexes. The lowest‐energy (longest‐wavelength) spin‐forbidden transition is studied for for [Ir(pbt)2(acac)] and [Re(CO)4(pbt)] and the complexes [W(CO)4(bpy)] and [Mo(CO)4(bpy)]. For the latter complexes, spin‐forbidden transitions from higher spin‐triplet levels are additionally analyzed. SO‐NTOs are compared with spin‐free NTOs for the transitions under consideration. The major assignment of a spin‐forbidden transition is obtained from the spin‐free NTO analysis, while the source of intensity of the electronic transition is revealed by the SO‐NTOs.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 2318763

Alternate ID(s):: OSTI ID: 2472086

Journal Information:: ChemistryOpen, Journal Name: ChemistryOpen; ISSN 2191-1363

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (47)

Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
Sustainable metal complexes for organic light-emitting diodes (OLEDs) Bizzarri, Claudia; Spuling, Eduard; Knoll, Daniel M. Coordination Chemistry Reviews, Vol. 373 https://doi.org/10.1016/j.ccr.2017.09.011	journal	October 2018
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory Granovsky, Alexander A. The Journal of Chemical Physics, Vol. 134, Issue 21 https://doi.org/10.1063/1.3596699	journal	June 2011
Geometry optimizations in the zero order regular approximation for relativistic effects van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan The Journal of Chemical Physics, Vol. 110, Issue 18 https://doi.org/10.1063/1.478813	journal	May 1999
Predicting phosphorescent lifetimes and zero-field splitting of organometallic complexes with time-dependent density functional theory including spin–orbit coupling Mori, K.; Goumans, T. P. M.; van Lenthe, E. Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C3CP55438D	journal	January 2014
Unbiased auxiliary basis sets for accurate two-electron integral approximations Aquilante, Francesco; Lindh, Roland; Bondo Pedersen, Thomas The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2777146	journal	September 2007
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Exact decoupling of the relativistic Fock operator Peng, Daoling; Reiher, Markus Theoretical Chemistry Accounts, Vol. 131, Issue 1 https://doi.org/10.1007/s00214-011-1081-y	journal	January 2012
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
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
The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs Yersin, Hartmut; Rausch, Andreas F.; Czerwieniec, Rafał Coordination Chemistry Reviews, Vol. 255, Issue 21-22 https://doi.org/10.1016/j.ccr.2011.01.042	journal	November 2011
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
[M(CO) ₄ (2,2′-bipyridine)] (M=Cr, Mo, W) Complexes as Efficient Catalysts for Electrochemical Reduction of CO ₂ at a Gold Electrode Tory, Joanne; Setterfield-Price, Briony; Dryfe, Robert A. W. ChemElectroChem, Vol. 2, Issue 2 https://doi.org/10.1002/celc.201402282	journal	September 2014
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
Quantitative El-Sayed Rules for Many-Body Wave Functions from Spinless Transition Density Matrices Pokhilko, Pavel; Krylov, Anna I. The Journal of Physical Chemistry Letters, Vol. 10, Issue 17 https://doi.org/10.1021/acs.jpclett.9b02120	journal	August 2019
The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry Li Manni, Giovanni; Fdez. Galván, Ignacio; Alavi, Ali Journal of Chemical Theory and Computation https://doi.org/10.1021/acs.jctc.3c00182	journal	May 2023
Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe Martin, Jan M. L.; Sundermann, Andreas The Journal of Chemical Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.1337864	journal	February 2001
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke Journal of Physical Chemistry A https://doi.org/10.1021/jp031064	journal	December 2003
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Multiconfiguration Pair-Density Functional Theory Li Manni, Giovanni; Carlson, Rebecca K.; Luo, Sijie Journal of Chemical Theory and Computation, Vol. 10, Issue 9 https://doi.org/10.1021/ct500483t	journal	August 2014
Energy-adjustedab initio pseudopotentials for the second and third row transition elements Andrae, D.; H�u�ermann, U.; Dolg, M. Theoretica Chimica Acta, Vol. 77, Issue 2 https://doi.org/10.1007/BF01114537	journal	January 1990
Luminescence properties of organometallic complexes Lees, Alistair J. Chemical Reviews, Vol. 87, Issue 4 https://doi.org/10.1021/cr00080a003	journal	August 1987
The Complete Active Space Self-Consistent Field Method and its Applications in Electronic Structure Calculations Roos, Björn O. Advances in Chemical Physics https://doi.org/10.1002/9780470142943.ch7	book	January 1987
Calculation of spin–orbit couplings using RASCI spinless one-particle density matrices: Theory and applications Carreras, Abel; Jiang, Hanjie; Pokhilko, Pavel The Journal of Chemical Physics, Vol. 153, Issue 21 https://doi.org/10.1063/5.0029146	journal	December 2020
OpenMolcas: From Source Code to Insight Fdez. Galván, Ignacio; Vacher, Morgane; Alavi, Ali Journal of Chemical Theory and Computation, Vol. 15, Issue 11 https://doi.org/10.1021/acs.jctc.9b00532	journal	September 2019
Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients Shiozaki, Toru; Győrffy, Werner; Celani, Paolo The Journal of Chemical Physics, Vol. 135, Issue 8 https://doi.org/10.1063/1.3633329	journal	August 2011
Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re ₂ Cl ₈ ^2– Carlson, Rebecca K.; Truhlar, Donald G.; Gagliardi, Laura Journal of Chemical Theory and Computation, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jctc.5b00609	journal	August 2015
A mean-field spin-orbit method applicable to correlated wavefunctions Heß, Bernd A.; Marian, Christel M.; Wahlgren, Ulf Chemical Physics Letters, Vol. 251, Issue 5-6 https://doi.org/10.1016/0009-2614(96)00119-4	journal	March 1996
A Nonorthogonal State-Interaction Approach for Matrix Product State Wave Functions Knecht, Stefan; Keller, Sebastian; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 12, Issue 12 https://doi.org/10.1021/acs.jctc.6b00889	journal	November 2016
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Photophysical properties of Re(pbt)(CO)4 studied by high resolution spectroscopy Czerwieniec, Rafał; Finkenzeller, Walter J.; Hofbeck, Thomas Chemical Physics Letters, Vol. 468, Issue 4-6 https://doi.org/10.1016/j.cplett.2008.11.086	journal	January 2009
Quantitative wave function analysis for excited states of transition metal complexes Mai, Sebastian; Plasser, Felix; Dorn, Johann Coordination Chemistry Reviews, Vol. 361 https://doi.org/10.1016/j.ccr.2018.01.019	journal	April 2018
Calculation of transition density matrices by nonunitary orbital transformations Malmqvist, Per �ke International Journal of Quantum Chemistry, Vol. 30, Issue 4 https://doi.org/10.1002/qua.560300404	journal	October 1986
Modern quantum chemistry with [Open]Molcas Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0004835	journal	June 2020
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
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
The restricted active space (RAS) state interaction approach with spin–orbit coupling Malmqvist, Per Åke; Roos, Björn O.; Schimmelpfennig, Bernd Chemical Physics Letters, Vol. 357, Issue 3-4 https://doi.org/10.1016/S0009-2614(02)00498-0	journal	May 2002
Multiple Anti-Kasha Emissions in Transition-Metal Complexes Röhrs, Milena; Escudero, Daniel The Journal of Physical Chemistry Letters, Vol. 10, Issue 19 https://doi.org/10.1021/acs.jpclett.9b02477	journal	September 2019
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
Quantum Chemistry of d- and f-Block Elements Autschbach, Jochen Comprehensive Computational Chemistry https://doi.org/10.1016/B978-0-12-821978-2.00134-3	book	October 2023
Electronic structure in the transition metal block and its implications for light harvesting McCusker, James K. Science, Vol. 363, Issue 6426 https://doi.org/10.1126/science.aav9104	journal	January 2019
Spin–Orbit Natural Transition Orbitals and Spin-Forbidden Transitions Feng, Rulin; Yu, Xiaojuan; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 17, Issue 12 https://doi.org/10.1021/acs.jctc.1c00776	journal	November 2021
The CASSCF state interaction method Malmqvist, Per-Åke; Roos, Björn O. Chemical Physics Letters, Vol. 155, Issue 2 https://doi.org/10.1016/0009-2614(89)85347-3	journal	February 1989
Photochemistry of transition metal coordination compounds Adamson, A. W. Pure and Applied Chemistry, Vol. 20, Issue 1 https://doi.org/10.1351/pac196920010025	journal	January 1969
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) Yanai, Takeshi; Tew, David P.; Handy, Nicholas C. Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57 https://doi.org/10.1016/j.cplett.2004.06.011	journal	July 2004
Fine tuning of emission color of iridium(iii) complexes from yellow to red via substituent effect on 2-phenylbenzothiazole ligands: synthesis, photophysical, electrochemical and DFT study Li, Ming; Zeng, Hui; Meng, Yanyan Dalton Transactions, Vol. 40, Issue 27 https://doi.org/10.1039/c1dt10305a	journal	January 2011

Similar Records

Hydrosilane σ‐Adduct Intermediates in an Adaptive Zinc‐Catalyzed Cross‐dehydrocoupling of Si−H and O−H Bonds

Journal Article · 2021 · Chemistry - A European Journal · OSTI ID:1784396

Patnaik, Smita; Kanbur, Uddhav; Ellern, Arkady; +1 more

Scaling Behavior of Thermally Driven Fractures in Deep Low‐Permeability Formations: A Plane Strain Model With 1‐D Heat Conduction

Journal Article · 2022 · Journal of Geophysical Research. Solid Earth · OSTI ID:1846323

Chen, Bin; Zhou, Quanlin

Impact of Changing Winds on the Mauna Loa CO ₂ Seasonal Cycle in Relation to the Pacific Decadal Oscillation

Journal Article · 2022 · Journal of Geophysical Research: Atmospheres · OSTI ID:1874724

Jin, Yuming; Keeling, Ralph F.; Rödenbeck, Christian; +3 more

Title: Triplet‐Singlet Emission of d‐Block Metal Complexes Characterized by Spin‐Orbit Natural Transition Orbitals

Citation Formats

References (47)

Similar Records

Related Subjects