Spin-orbit induced radiationless transitions in organometallics: Quantum simulation of the intersystem crossing processes in the photodissociation of HCo(CO)4

Heitz, Marie-Catherine; Ribbing, Carl G.; Daniel, Chantal

doi:10.1063/1.473291

Cited by 51 publications

(36 citation statements)

References 25 publications

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“…A few studies have been published that go beyond the golden rule approximation and treat ISC processes dynamically. In the work of Daniel et al,160 radiationless transitions of organometallic complexes were simulated by wave packet propagation along one‐dimensional reaction coordinates on spin–orbit‐coupled potential energy surfaces. The underlying zero‐order functions were pure‐spin Born–Oppenheimer states corresponding to a diabatic representation in C 3 v symmetry.…”

Section: Intersystem Crossing Ratesmentioning

confidence: 99%

Spin–orbit coupling and intersystem crossing in molecules

Marian

2011

WIREs Comput Mol Sci

726

799

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Many light‐induced molecular processes involve a change in spin state and are formally forbidden in non‐relativistic quantum theory. To make them happen, spin–orbit coupling (SOC) has to be invoked. Intersystem crossing (ISC), the nonradiative transition between two electronic states of different multiplicity, plays a key role in photochemistry and photophysics with a broad range of applications including molecular photonics, biological photosensors, photodynamic therapy, and materials science. Quantum chemistry has become a valuable tool for gaining detailed insight into the mechanisms of ISC. After a short introduction highlighting the importance of ISC and a brief description of the relativistic origins of SOC, this article focusses on approximate SOC operators for practical use in molecular applications and reviews state‐of‐the‐art theoretical methods for evaluating ISC rates. Finally, a few sample applications are discussed that underline the necessity of studying the mechanisms of ISC processes beyond qualitative rules such as the El‐Sayed rules and the energy gap law. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Structure and Mechanism > Molecular Structures

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Section: Intersystem Crossing Ratesmentioning

confidence: 99%

Spin–orbit coupling and intersystem crossing in molecules

Marian

2011

WIREs Comput Mol Sci

726

799

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“…1 Far from being a curiosity, ISC plays an important role in the deactivation process of organic molecules [2][3][4] and metal complexes 5 that are used in energyrelated devices. 6,7 Apart from grid-based exact quantum dynamics for low dimensional problems, 8 few nonadiabatic dynamics methods have been extended to include SOC effects and, therefore, to describe ISC. 9 As one example, the Multiconfiguration Time-Dependent Hartree (MCTDH) technique has been used to understand the role of intersystem crossing in benzene photophysics.…”

Section: Introductionmentioning

confidence: 99%

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Curchod

Rauer

Marquetand

et al. 2016

The Journal of Chemical Physics

104

103

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A new approach to molecular dynamics with non-adiabatic and spin-orbit effects with applications to QM/MM simulations of thiophene and selenophene The Journal of Chemical Physics 146, 114101 (2017); 10.1063/1.4978289 THE JOURNAL OF CHEMICAL PHYSICS 144, 101102 (2016) Communication: GAIMS-Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation. C 2016 AIP Publishing LLC. [http://dx

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“…* M-R ; R¼ ¼H or CH 3 ) photoactive for the CO dissociation observed upon UV irradiation of the hydrides. 27,28 In contrast, the first nearly pure MSBCT state is calculated at 42,795 cm À1 with a null oscillator strength and should not play a role in the observed photochemistry. Small contributions of MSBCT character appear in CH 3 Mn(CO) 5 in low-lying a 1 A@, c 1 A@, and d 1 A@ states, but as shown in the next section they do not contribute to ligand dissociation.…”

Section: Vertical Transition Energies and Absorption Spectrum Assignmentmentioning

confidence: 92%

“…16,17 The aim of the present study is in line with our previous work based on quantum chemistry and wavepacket dynamics, reporting the mechanism of concurrent primary photochemical reactions in organometallics. [27][28][29][30] One important goal of these investigations is to find a suitable molecular system where to perform ultrafast laser control experiments in the weak field regime and to correlate with theoretical quantum dynamical simulations. The first step is the assignment of the electronic absorption spectrum and the construction of state correlation diagrams to identify the photoactive excited states and the dissociative channels.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of CH₃Mn(CO)₅: A multiconfigurational ab initio study

González

Daniel

2006

J Comput Chem

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The electronic spectroscopy of CH3Mn(CO)5 has been investigated by means of ab initio multiconfigurational MS-CASPT2/CASSCF calculations. The absorption spectrum is characterized by a series of Metal-Centered (MC) excited states in the UV energy domain (below 290 nm) that could be responsible for the observed photoreactivity starting at 308 nm. The upper part of the spectrum is overcrowded between 264 and 206 nm and dominated by a high density of Metal-to-Ligand-Charge-Transfer (MLCT) states corresponding mainly to 3d(Mn) --> pi*(CO) excitations. A non-negligible contribution of Metal-to-sigma-Bond-Charge-Transfer (MSBCT) states corresponding to 3d(Mn) --> sigma*(Mn-CH3) excitations is also present in the theoretical spectrum of CH3Mn(CO)5. However, in contrast to other transition metal hydrides and methyl substituted (HMn(CO)5, HCo(CO)4, and CH3Co(CO)4) these MSBCT transitions do not participate to the lowest bands of the spectrum as main contributions. The photochemistry of CH3Mn(CO)5, namely the loss of a CO ligand vs. the metal-methyl bond homolysis, is investigated by means of MS-CASPT2 states correlation diagrams. This study illustrates the complexity of the photodissociation mechanism of this class of molecules, which involves a large number of nearly degenerate electronic states with several channels for fragmentation.

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Spin-orbit induced radiationless transitions in organometallics: Quantum simulation of the intersystem crossing processes in the photodissociation of HCo(CO)4

Cited by 51 publications

References 25 publications

Spin–orbit coupling and intersystem crossing in molecules

Spin–orbit coupling and intersystem crossing in molecules

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Photochemistry of CH₃Mn(CO)₅: A multiconfigurational ab initio study

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Spin-orbit induced radiationless transitions in organometallics: Quantum simulation of the intersystem crossing processes in the photodissociation of HCo(CO)4

Cited by 51 publications

References 25 publications

Spin–orbit coupling and intersystem crossing in molecules

Spin–orbit coupling and intersystem crossing in molecules

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Photochemistry of CH3Mn(CO)5: A multiconfigurational ab initio study

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Photochemistry of CH₃Mn(CO)₅: A multiconfigurational ab initio study