Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)42+

Pižl, Martin; Hunter, Bryan M.; Greetham, Gregory M.; Towrie, Michael; Záliš, Stanislav; Gray, Harry B.; Vlček, Antonı́n

doi:10.1021/acs.jpca.7b10215

Cited by 5 publications

(1 citation statement)

References 33 publications

(127 reference statements)

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“…For example, spin-phonon coupling plays a major role in the photophysical and photochemical properties of transition metal complexes, including ultrafast spin state switching and intersystem crossing, wherein it provides a strong influence on nonequilibrium dynamics. [1][2][3][4][5] It is also a major factor in the magnetization dynamics of single molecule magnets [6][7][8][9] and coherent materials for quantum information science. [10][11][12][13][14][15][16] Beyond molecular systems, spin-phonon coupling also plays important roles in extended solids and condensed matter (e.g., transition metal oxides) by giving rise to emergent phenomena such as colossal magnetoresistance and high TC superconductivity, [17][18][19][20][21][22] including vibrational or optical control of these properties.…”

Section: Introductionmentioning

confidence: 99%

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

Mirzoyan¹,

Hadt²

2019

Preprint

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Quantum coherence of S = 1/2 transition metal-based quantum bits (qubits) is strongly influenced by the magnitude of spin–phonon coupling. While this coupling is recognized as deriving from dynamic distortions about the first coordination sphere of the metal, a general model for understanding and quantifying ligand field contributions has not been established. Here we derive a general ligand field theory model to describe and quantify the nature of spin–phonon coupling terms in S = 1/2 transition metal complexes. We show that the coupling term for a given vibrational mode is governed by: 1) the magnitude of the metal-based spin–orbit coupling constant, 2) the magnitude and gradient in the ligand field excited state energy, and 3) dynamic relativistic nephelauxetic contributions reflecting the magnitude and gradient in the covalency of the ligand–metal bonds. From an extensive series of density functional theory (DFT) and time-dependent DFT (TDDFT) calculations calibrated to a range of experimental data, spin–phonon coupling terms describing minimalistic D4h/D2d [CuCl4]2- and C4v [VOCl4]2- complexes translate to and correlate with experimental quantum coherence properties observed for Cu(II)- and V(IV)-based molecular qubits with different ligand sets, geometries, and coordination numbers. While providing a fundamental framework and means to benchmark current qubits, the model and methodology described herein can be used to screen any S = 1/2 molecular qubit candidate and guide the discovery of room temperature coherent materials for quantum information processing.

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Section: Introductionmentioning

confidence: 99%

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

Mirzoyan¹,

Hadt²

2019

Preprint

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Excited-state dynamics of luminescent transition metal complexes with metallophilic and donor–acceptor interactions

Ito

Iwamura

Sakuda

2022

Coordination Chemistry Reviews

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Ultrafast Intersystem Crossing and Structural Dynamics of [Pt(ppy)(μ-^tBu₂pz)]₂

et al. 2020

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Intersystem crossing (ISC) rates of transition-metal complexes are determined by the complex interplay of a molecule’s electronic and structural dynamics. To broaden our understanding of these key factors, we investigate the case of the prototypical d8–d8 dimetal complex [Pt(ppy)(μ- t Bu2pz)]2 using broad-band transient absorption anisotropy in combination with ultrafast fluorescence up-conversion and ab initio calculations. We find that, upon excitation of the molecule’s metal–metal-to-ligand charge-transfer transition, ISC occurs in hundreds of femtoseconds from the lowest excited singlet state S1 to the triplet state T2, from where the energy relaxes to the lowest energy triplet state T1. ISC to the T2 state, rather than T1, is further rationalized through supporting arguments. Observed vibrational coherences along the Pt–Pt mode are attributed to the formation of nuclear wavepackets on the ground and excited electronic states that dephase prior to ISC because of the structural flexibility of the complex. Beyond demonstrating the relationship between the energy relaxation and structural dynamics of [Pt(ppy)(μ- t Bu2pz)]2, our results provide new insights into the photoinduced dynamics of d8–d8 dimetal complexes more generally.

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Ultrafast Wiggling and Jiggling: Ir₂(1,8-diisocyanomenthane)₄²⁺

Abstract: 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

Cited by 5 publications

References 33 publications

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

Excited-state dynamics of luminescent transition metal complexes with metallophilic and donor–acceptor interactions

Ultrafast Intersystem Crossing and Structural Dynamics of [Pt(ppy)(μ-^tBu₂pz)]₂

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Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)42+

Abstract: 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59

Cited by 5 publications

References 33 publications

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

The Dynamic Ligand Field of a Molecular Qubit: Decoherence Through Spin–Phonon Coupling

Excited-state dynamics of luminescent transition metal complexes with metallophilic and donor–acceptor interactions

Ultrafast Intersystem Crossing and Structural Dynamics of [Pt(ppy)(μ-tBu2pz)]2

Contact Info

Product

Resources

About

Ultrafast Wiggling and Jiggling: Ir₂(1,8-diisocyanomenthane)₄²⁺

Ultrafast Intersystem Crossing and Structural Dynamics of [Pt(ppy)(μ-^tBu₂pz)]₂