Model of Ultrafast Intersystem Crossing in Photoexcited Transition-Metal Organic Compounds

Veenendaal, Michel van; Chang, Jun; Fedro, A. J.

doi:10.1103/physrevlett.104.067401

Cited by 61 publications

(74 citation statements)

References 17 publications

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“…This seems to be unaffordable even considering the possibility that the molecule may be in a vibrational excited state due to interaction with the surroundings. The mechanism proposed by Chang et al [58,59] limits the energy difference between 3 MLCT and 5 MLCT states to the interval 0.12 − 0.68 eV, with the 5 MLCT lower in energy as suggested by Figure 1 of Ref. [59].…”

Section: Deactivation Involving the 5 Mlct Statesmentioning

confidence: 92%

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃

Graaf

Sousa

2011

Int J of Quantum Chemistry

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ABSTRACT:The light-induced spin crossover in Fe II complexes is studied with complete active space second-order perturbation theory. The potential energy surfaces of the low-spin and high-spin states are determined as function of the Fe-ligand distance interpolating between the high-spin and low-spin equilibrium geometries. In addition, we calculate the relative energies of the lowest excited Fe-3d 6 states along this coordinate. To address the mechanism of spin crossover, the metal-to-ligand charge transfer states with singlet, triplet, and quintet spin coupling were also treated. The curves of the singlet and triplet MLCT states nearly coincide, but the quintet MLCT curve is higher in energy and the equilibrium distance displaced to larger distances. The possible deactivation mechanisms of the 1 MLCT state are discussed considering the relative energies and spin-orbit coupling matrix elements of the relevant electronic states.

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Section: Deactivation Involving the 5 Mlct Statesmentioning

confidence: 92%

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃

Graaf

Sousa

2011

Int J of Quantum Chemistry

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“…Firstly, these materials display signatures of strong spin-orbit coupling (SOC): most notably phosphorescent decay and fast intersystem crossing, [8] which are both mediated by SOC. This has motivated several groups to include SOC in their calculations.…”

Section: Triazolyl)iridium(iii)mentioning

confidence: 99%

Spin–Orbit Coupling in Phosphorescent Iridium(III) Complexes

2011

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We study the excited states of two iridium(III) complexes with potential applications in organic light-emitting diodes: fac-tris(2-phenylpyridyl)iridium(III) [Ir(ppy)(3)] and fac-tris(1-methyl-5-phenyl-3-n-propyl-[1,2,4]triazolyl)iridium(III) [Ir(ptz)(3)]. Herein we report calculations of the excited states of these complexes from time-dependent density functional theory (TDDFT) with the zeroth-order regular approximation (ZORA). We show that results from the one-component formulation of ZORA, with spin-orbit coupling included perturbatively, accurately reproduce both the results of the two-component calculations and previously published experimental absorption spectra of the complexes. We are able to trace the effects of both scalar relativistic correction and spin-orbit coupling on the low-energy excitations and radiative lifetimes of these complexes. In particular, we show that there is an indirect relativistic stabilisation of the metal-to-ligand charge transfer (MLCT) states. This is important because it means that indirect relativistic effects increase the degree to which SOC can hybridise singlet and triplet states and hence plays an important role in determining the optical properties of these complexes. We find that these two compounds are remarkably similar in these respects, despite Ir(ppy)(3) and Ir(ptz)(3) emitting green and blue light respectively. However, we predict that these two complexes will show marked differences in their magnetic circular dichroism (MCD) spectra.

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“…[4][5][6] This phenomenon, called Light-Induced Excited Spin State Trapping (LIESST), initially found in Fe(II) complexes [7][8][9][10][11] and later also observed in systems containing Fe(III), [12][13][14][15] and Ni(II) [16][17][18] has been intensively studied in the last years in order to unravel its mechanism both with experimental techniques 11,[19][20][21][22][23][24][25] and by means of theoretical calculations. [26][27][28][29][30][31][32][33] The most numerous and most studied family of SCO systems involves octahedral Fe(II) complexes in the solid state or in solution. The LS-HS transition in Fe(II) complexes is accompanied by an enlargement of the iron-ligand distances due to the occupation of antibonding e orbitals in the HS state.…”

Section: Introductionmentioning

confidence: 99%

Computational approach to the study of thermal spin crossover phenomena

Rudavskyi

Sousa

Graaf

et al. 2014

The Journal of Chemical Physics

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The key parameters associated to the thermally induced spin crossover process have been calculated for a series of Fe(II) complexes with mono-, bi-, and tridentate ligands. Combination of density functional theory calculations for the geometries and for normal vibrational modes, and highly correlated wave function methods for the energies, allows us to accurately compute the entropy variation associated to the spin transition and the zero-point corrected energy difference between the low-and high-spin states. From these values, the transition temperature, T 1/2 , is estimated for different compounds.

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Model of Ultrafast Intersystem Crossing in Photoexcited Transition-Metal Organic Compounds

Cited by 61 publications

References 17 publications

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃

Spin–Orbit Coupling in Phosphorescent Iridium(III) Complexes

Computational approach to the study of thermal spin crossover phenomena

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Model of Ultrafast Intersystem Crossing in Photoexcited Transition-Metal Organic Compounds

Cited by 61 publications

References 17 publications

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in FeII (bpy)3

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in FeII (bpy)3

Spin–Orbit Coupling in Phosphorescent Iridium(III) Complexes

Computational approach to the study of thermal spin crossover phenomena

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Product

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On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃

On the role of the metal‐to‐ligand charge transfer states in the light‐induced spin crossover in Fe^II (bpy)₃