Intersystem Crossings in Late-Row Elements: A Perspective

Valentine, Andrew J. S.; Li, Xiaosong

doi:10.1021/acs.jpclett.2c00207

Cited by 14 publications

(15 citation statements)

References 81 publications

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“…In this work, we compared the results of the four-component and exact two-component (X2C) − calculations. Recently, the X2C method has been shown to accurately model the X-ray absorption spectra and intersystem crossing transitions in molecules containing late-row elements. , In our study, we find that the energy gaps between the states calculated using the four- and two-component methods agree within 9 cm –1 (Table S3), indicating the high accuracy of the variational X2C method. We also compare the results of the variational SOC calculations with those obtained using the conventional perturbative SOC approach, as implemented in the GAMESS and OpenMolcas suite of programs.…”

supporting

confidence: 63%

Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Dergachev

Nakritskaia

Varganov

2022

J. Phys. Chem. Lett.

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Lanthanide-based single-molecule magnets (SMMs) are promising building blocks for quantum memory and spintronic devices. Designing lanthanide-based SMMs with long spin relaxation time requires a detailed understanding of their electronic structure, including the crucial role of the spin–orbit coupling (SOC). While traditional calculations of SOC using the perturbation theory applied to a solution of the nonrelativistic Schrödinger equation are valid for light atoms, this approach is questionable for systems containing heavy elements such as lanthanides. We investigate the accuracy of the perturbation estimates of SOC by variationally solving the Dirac equation for the [DyO]+ molecule, a prototype of a lanthanide-based SMM. We show that the energy splittings between the states involved in spin relaxation depend on the interplay between strong SOC and dynamic electron correlation. We demonstrate that this interplay affects the resonances between the spin and vibrational transitions and, therefore, the spin relaxation time.

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supporting

confidence: 63%

Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Dergachev

Nakritskaia

Varganov

2022

J. Phys. Chem. Lett.

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“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.2c00659. (2), where G is the spatial symmetry group of the molecule. States with large singlet-triplet mixing is written as a direct sum of the singlet and triplet irreducible representations.…”

Section: * Sı Supporting Informationmentioning

confidence: 99%

“…Spin–orbit coupling (SOC) is a cornerstone of modern chemistry, responsible for important photochemical phenomena such as intersystem crossing, , relativistic spectroscopies (for example, L-edge X-ray absorption, magnetic circular dichroism), and fine-structure splitting . Taking advantage of spin-forbidden processes allowed by SOC has contributed to recent advances throughout chemistry and materials science, especially in LED and solar cell technology. , With growing popularity in exploring spin-forbidden processes and the ubiquity of nonmain group elements in modern chemistry, there is demand for an efficient SOC method suitable for atomically diverse and large systems.…”

Section: Introductionmentioning

confidence: 99%

State Interaction Linear Response Time-Dependent Density Functional Theory with Perturbative Spin–Orbit Coupling: Benchmark and Perspectives

Liao

Kasper

Jenkins

et al. 2023

JACS Au

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Spin–orbit coupling (SOC) is an important driving force in photochemistry. In this work, we develop a perturbative spin–orbit coupling method within the linear response time-dependent density function theory framework (TDDFT-SO). A full state interaction scheme, including singlet–triplet and triplet–triplet coupling, is introduced to describe not only the coupling between the ground and excited states, but also between excited states with all couplings between spin microstates. In addition, expressions to compute spectral oscillator strengths are presented. Scalar relativity is included variationally using the second-order Douglas-Kroll-Hess Hamiltonian, and the TDDFT-SO method is validated against variational SOC relativistic methods for atomic, diatomic, and transition metal complexes to determine the range of applicability and potential limitations. To demonstrate the robustness of TDDFT-SO for large-scale chemical systems, the UV–Vis spectrum of Au25(SR)18 – is computed and compared to experiment. Perspectives on the limitation, accuracy, and capability of perturbative TDDFT-SO are presented via analyses of benchmark calculations. Additionally, an open-source Python software package () is developed and released to interface with the Gaussian 16 quantum chemistry software package to perform this calculation.

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“…The nonradiative intramolecular energy transfer (IET) process (also called antenna effect ) is broadly exploited to increase the brightness of luminescent metal complexes, in particular for trivalent lanthanide ions when, for example, these molecules are employed as optical probes for imaging − and luminescent sensing. − For such a class of compounds, brightness is defined as B = ε · ϕ ovl = ε · η sens · ϕ int , where ε is the molar absorption coefficient, ϕ ovl is the overall quantum yield, i.e., the ratio of emitting/absorbed photons by the matrix/ligand, η sens is the overall energy transfer efficiency, and ϕ int is the intrinsic quantum yield, i.e., the ratio of emitting/absorbed photons upon direct excitation into a luminescent level of the lanthanide ion. Thus, to obtain high values of brightness, the combination of high ε, η sens , and ϕ int values is required (η sens = η ISC · η IET ; where η ISC and η IET are the efficiency of the intersystem crossing (ISC) and the IET processes, respectively). In this direction, one should avoid nonradiative processes, which negatively impact the ϕ int value.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

et al. 2022

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In this work, we investigated from a theoretical point of view the dynamics of the energy transfer process from the ligand to Eu(III) ion for 12 isomeric species originating from six different complexes differing by nature of the ligand and the total charge. The cationic complexes present the general formula [Eu(L)(H2O)2]+ (where L = bpcd2– = N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate; bQcd2– = N,N′-bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate; and bisoQcd2– = N,N′-bis(2-isoquinolinmethyl)-trans-1,2-diaminocyclohexane N,N′-diacetate), while the neutral complexes present the Eu(L)(H2O)2 formula (where L = PyC3A3– = N-picolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; QC3A3– = N-quinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate; and isoQC3A3– = N-isoquinolyl-N,N′,N′-trans-1,2-cyclohexylenediaminetriacetate). Time-dependent density functional theory (TD-DFT) calculations provided the energy of the ligand excited donor states, distances between donor and acceptor orbitals involved in the energy transfer mechanism (R L), spin-orbit coupling matrix elements, and excited-state reorganization energies. The intramolecular energy transfer (IET) rates for both singlet-triplet intersystem crossing and ligand-to-metal (and vice versa) involving a multitude of ligand and Eu(III) levels and the theoretical overall quantum yields (ϕovl) were calculated (the latter for the first time without the introduction of experimental parameters). This was achieved using a blend of DFT, Judd–Ofelt theory, IET theory, and rate equation modeling. Thanks to this study, for each isomeric species, the most efficient IET process feeding the Eu(III) excited state, its related physical mechanism (exchange interaction), and the reasons for a better or worse overall energy transfer efficiency (ηsens) in the different complexes were determined. The spectroscopically measured ϕovl values are in good agreement with the ones obtained theoretically in this work.

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Intersystem Crossings in Late-Row Elements: A Perspective

Cited by 14 publications

References 81 publications

Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

State Interaction Linear Response Time-Dependent Density Functional Theory with Perturbative Spin–Orbit Coupling: Benchmark and Perspectives

Dynamics of the Energy Transfer Process in Eu(III) Complexes Containing Polydentate Ligands Based on Pyridine, Quinoline, and Isoquinoline as Chromophoric Antennae

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