Jahn–Teller effects in initial and final states: high-resolution X-ray absorption, photoelectron and Auger spectroscopy of allene

Muchová, Eva; Hollas, Daniel; Holland, D.M.P.; Bacellar, Camila; Leroy, Ludmila; Barillot, T.; Longetti, Luca; Coreno, Marcello; Simone, Monica de; Grazioli, Cesare; Chergui, Majed; Ingle, Rebecca A.

doi:10.1039/d2cp05299g

Cited by 7 publications

(10 citation statements)

References 106 publications

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“…[53] The active space of 3 electrons in 2 active orbitals (singly occupied molecular orbital (SOMO) and doubly occupied molecular orbital (HDMO)) is chosen because these are sufficient to reproduce the emission energies utilizing the ∆SCF approach with PBE0-D3(BJ)/def2-SVP (see Figure S7). [36][37][38][39][40][41][42][43][44][45] Here the transition of the spin-down electron from HDMO to SOMO matches the experimentally observed emission energy (see also Supporting Information for further clarification).…”

Section: Quantum Chemical Calculations On the Photophysicssupporting

confidence: 78%

“…We optimize their ground (D0) with Kohn-Sham DFT and first excited state (D1) geometries using ∆SCF initial maximum overlap method ((IMOM-), both at the PBE0-D3(BJ)/def2-SVP level. [36][37][38][39][40][41][42][43][44][45] We determine the canonical orbitals involved in the transition using (∆SCF -)PBE0-D3(BJ)/def2-SVP (see Figure 3). These are the highest occupied spin-down orbitals in D0 and D1.…”

Section: Excited State Characteristicsmentioning

confidence: 99%

“…According to the quantum chemical calculations for molecule 33, at the ∆SCF-DFT level the relaxation of the excited state to the D1 minimum proceeds via a barrierless rotation around the donor-TTM bond with no state crossing involved. [36][37][38][39][40][41][42][43][44][45] Involvement of two separate adiabatic states that represent the LE and CT state, was also ruled out by means of TD-DFT calculations. Hence, for medium-strength donors, we assume almost instantaneous relaxation of the locally excited D1 state (found vertically at the D0 minimum) to a relaxed state with more pronounced CT character.…”

Section: Excited State Characteristicsmentioning

confidence: 99%

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On the Effect of Donor Strength on the Photoluminescence Performance in Mono-substituted N-Donor Triarylmethyl Radicals

Arnold,

Ross,

Thielert

et al. 2024

Preprint

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The functionalization of light-emitting triarylmethyl radicals with electron donating moieties can significantly increase their photoluminescence quantum yield . As luminophores in light-emitting diodes, such open-shell radicals can be used to overcome the problem of spin-statistics inherent to conventional closed-shell emitters. However, so far the functionalization of triarylmethyl radicals with donors of varying strength has been limited by the restricted reactivity of the triarylmethyl radical, constraining optimization of performance to empirical trial and error approaches. Here, we make use of the reliable reactivity of N-heterocyclic donors in radical-mediated aromatic substitutions, allowing us to systematically investigate the effect of donor strength on the emission characteristics of triarylmethyl radicals. As a single descriptor proxy to the donor strength, we employ the ionization energy IE of the donor moiety determined by density functional theory calculations. A systematic bathochromic shift of the emission wavelength \lambda_max is observed for increasing donor strength, while maximum \phi values are obtained for medium-strength donors. We rationalize these effects with a simple model based on the Marcus theory supported by quantum chemical calculations and electron paramagnetic resonance. This allows us to understand the effect of the donor strength on both \lambda_max and \phi, enabling the design of improved light-emitting radicals in the future.

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Section: Quantum Chemical Calculations On the Photophysicssupporting

confidence: 78%

Section: Excited State Characteristicsmentioning

confidence: 99%

Section: Excited State Characteristicsmentioning

confidence: 99%

See 1 more Smart Citation

On the Effect of Donor Strength on the Photoluminescence Performance in Mono-substituted N-Donor Triarylmethyl Radicals

Arnold,

Ross,

Thielert

et al. 2024

Preprint

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“…Here, we employ the core-valence separation (CVS) approximation, , which allows us to efficiently compute core-excited states by neglecting their interaction with excitations from the remaining occupied orbitals. CVS has been widely used for simulating core-level excited states and X-ray absorption spectra in combination with a variety of electronic structure theories. ,,,,,,,,− …”

Section: Theorymentioning

confidence: 99%

Core-Excited States and X-ray Absorption Spectra from Multireference Algebraic Diagrammatic Construction Theory

Mazin

Sokolov

2023

J. Chem. Theory Comput.

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We report the development and benchmark of multireference algebraic diagrammatic construction theory (MR-ADC) for the simulations of core-excited states and X-ray absorption spectra (XAS). Our work features an implementation that incorporates core-valence separation into the strict and extended second-order MR-ADC approximations (MR-ADC(2) and MR-ADC(2)-X), providing efficient access to high-energy excited states without including inner-shell orbitals in the active space. Benchmark results on a set of small molecules indicate that at equilibrium geometries, the accuracy of MR-ADC is similar to that of single-reference ADC theory when static correlation effects are not important. In this case, MR-ADC(2)-X performs similarly to single- and multireference coupled cluster methods in reproducing the experimental XAS peak spacings. We demonstrate the potential of MR-ADC for chemical systems with multiconfigurational electronic structure by calculating the K-edge XAS spectrum of the ozone molecule with a multireference character in its ground electronic state and the dissociation curve of core-excited molecular nitrogen. For ozone, the MR-ADC results agree well with the data from experimental and previous multireference studies of ozone XAS, in contrast to the results of single-reference methods, which underestimate relative peak energies and intensities. The MR-ADC methods also predict the correct shape of the core-excited nitrogen potential energy curve, and are in good agreement with accurate calculations using driven similarity renormalization group approaches. These findings suggest that MR-ADC(2) and MR-ADC(2)-X are promising methods for the XAS simulations of multireference systems and pave the way for their efficient computer implementation and applications.

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“…38 and 39, and the method has been successfully used in numerous cases. [40][41][42][43][44][45][46] The ground state MD simulations were performed at the B3LYP/6-31+g* level using the quantum thermostat, 47,48 with the temperature set to 300 K. The total length of the simulation was 50 ps and the time step was set to 0.5 fs. Within the NEA approach, a larger set of 400 and a smaller set of 50 geometries were selected from the ground state MD.…”

Section: Experimental Methodsmentioning

confidence: 99%

Deconvolution of the X-ray absorption spectrum of trans-1,3-butadiene with resonant Auger spectroscopy

Holland,

Suchan,

Janoš

et al. 2024

Phys. Chem. Chem. Phys.

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Jahn–Teller effects in initial and final states: high-resolution X-ray absorption, photoelectron and Auger spectroscopy of allene

Abstract: Carbon K-edge resonant Auger spectra of gas-phase allene following excitation of the pre-edge 1s → π* transitions are presented and analysed with the support of EOM-CCSD/cc-pVTZ calculations.

Cited by 7 publications

References 106 publications

On the Effect of Donor Strength on the Photoluminescence Performance in Mono-substituted N-Donor Triarylmethyl Radicals

On the Effect of Donor Strength on the Photoluminescence Performance in Mono-substituted N-Donor Triarylmethyl Radicals

Core-Excited States and X-ray Absorption Spectra from Multireference Algebraic Diagrammatic Construction Theory

Deconvolution of the X-ray absorption spectrum of trans-1,3-butadiene with resonant Auger spectroscopy

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