Ab initio Study of the Electronic Structure of Zinc Oxide and its Ions, ZnO<sup>0,±</sup>. Ground and Excited States

Sakellaris, Constantine N.; Papakondylis, Aristotle; Mavridis, Aristides

doi:10.1021/jp104764d

Cited by 17 publications

(13 citation statements)

References 38 publications

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“…The experimentally observed vibronic progression gives the distortion in the Zn−O bond length of the excited geometry relative to that of the ground state, Δ r Zn−O =0.02 Å, which was obtained from the equation Δ r Zn−O

= \sqrt{ℏ S_{normalZ normaln - O} / 4 c π μ ν_{normalZ normaln - O}}

, where S Zn−O is the Huang–Rhys parameter, which was determined from the parameter ϵ 0‐ n (see the Supporting Information). The experimentally obtained Δ r Zn−O value of 0.02 Å is consistent with the calculated value Δ r Zn−O =|1.805 Å−1.858 Å|=0.053 Å, and correlates well with the computational results for the [Zn II −O] + molecule …”

Section: Figuresupporting

confidence: 88%

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

et al. 2017

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Although a terminal oxyl species bound to certain metal ions is believed to be the intermediate for various oxidation reactions, such as O-O bond generation in photosystem II (PSII), such systems have not been characterized. Herein, we report a stable Zn -oxyl species induced by an MFI-type zeolite lattice and its reversible reactivity with O at room temperature. Its intriguing characteristics were confirmed by in situ spectroscopic studies in combination with quantum-chemical calculations, namely analyses of the vibronic Franck-Condon progressions and the ESR signal features of both Zn -oxyl and Zn -ozonide species formed during this reversible process. Molecular orbital analyses revealed that the reversible reaction between a Zn -oxyl species and an O molecule proceeds via a radical O-O coupling-decoupling mechanism; the unpaired electron of the oxyl species plays a pivotal role in the O-O bond generation process.

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= \sqrt{ℏ S_{normalZ normaln - O} / 4 c π μ ν_{normalZ normaln - O}}

Section: Figuresupporting

confidence: 88%

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

et al. 2017

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“…The experimentally obtained Dr ZnÀO value of 0.02 is consistent with the calculated value Dr ZnÀO =j 1.805 À1.858 j= 0.053 ,a nd correlates well with the computational results for the [Zn II À O] + molecule. [12] Although the p-interaction between the metal and oxygen atoms is recognized as the essential interaction for metal-oxo complexes,o wing to the closed-shell structure of Zn II with [Ar](3d) 10 (4s) 0 ,nop-bonds are constructed to oxyl. TheO2p x and O2p y orbitals,w hich are oriented perpendicular to the Zn À Ob ond axis,s carcely overlap with the Zn 3d and 4p orbitals;n evertheless,t hey match in terms of symmetry.…”

Section: Terminaloxooroxyl(radical)complexesoftransitionmetalsmentioning

confidence: 99%

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

et al. 2017

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Although at erminal oxyl species bound to certain metal ions is believed to be the intermediate for various oxidation reactions,s uch as OÀOb ond generation in photosystem II (PSII), such systems have not been characterized. Herein, we report as table Zn II -oxyl species induced by an MFI-type zeolite lattice and its reversible reactivity with O 2 at room temperature.Its intriguing characteristics were confirmed by in situ spectroscopic studies in combination with quantumchemical calculations,namely analyses of the vibronic Franck-Condon progressions and the ESR signal features of both Zn IIoxyl and Zn II -ozonide species formed during this reversible process.Molecular orbital analyses revealed that the reversible reaction between aZ n II -oxyl species and an O 2 molecule proceeds via aradical O-O coupling-decoupling mechanism; the unpaired electron of the oxyl species playsapivotal role in the OÀOb ond generation process.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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“…Other 3d transition-metal/first-row-atom diatomic species have proven to have similar challenges. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] These studies illustrate the power of the MRCI approach, which has consistently been shown to be a reasonably robust way of investigating low-lying excited states of these systems to usually at least semi-quantitative accuracy when compared against experiment. However, the studies also demonstrate the limitations of even these very high accuracy methods, e.g.…”

Section: Introductionmentioning

confidence: 97%

Ab initiocalculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

2016

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Accurate knowledge of the rovibronic near-infrared and visible absorption spectra of transition metal diatomic species like vanadium monoxide (VO) is very important for studies of cool stellar and hot planetary atmospheres. Here, the required ab initio curves are produced for the dipole moment and spin-orbit coupling, both diagonal and off-diagonal. The reliability of these curves is estimated by comparing potential energy surfaces obtained using the same methodology against experimental data (e.g. excitation energies, vibrational frequencies, bond distances). The ab initio data produced here forms the basis of a new spectroscopic model for the rovibronic spectroscopy of VO. This model has been used to produce a new VO line list which considers 13 different electronic states and contains almost 640,000 energy levels and over 277 million transitions.Open shell transition metal diatomics are challenging species to model through ab initio quantum mechanics due to the large number of low-lying electronic states, significant relativistic effects (particularly strong spin-orbit coupling within and between electronic states) and strong static and dynamic electron correlation. Multi-reference configuration interaction (MRCI) methodologies using orbitals from a complete active space self-consistent-field (CASSCF) calculation are the standard technique for this kinds of system. We use different state-specific or minimal-state CASSCF orbitals for each electronic state to maximise the accuracy of the calculation. We demonstrate that this choice of orbitals significantly affects the quality of the property calculations by comparing results using CASSCF orbitals optimised for different numbers of states.The off-diagonal dipole moment, or the transition moment, is the critical property controlling the intensity of electronic transitions. We test the use of finite-field off-diagonal dipole moments, but found that (1) the accuracy of the excitation energies were not sufficient to allow accurate dipole moments to be evaluated and (2) computer time requirements for perpendicular transitions were prohibitive. The best off-diagonal dipole moments are calculated using wavefunctions with different CASSCF orbitals.

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Ab initio Study of the Electronic Structure of Zinc Oxide and its Ions, ZnO^0,±. Ground and Excited States

Cited by 17 publications

References 38 publications

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

Ab initiocalculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

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Ab initio Study of the Electronic Structure of Zinc Oxide and its Ions, ZnO0,±. Ground and Excited States

Cited by 17 publications

References 38 publications

Identification of a Stable ZnII–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O2 at Room Temperature

Identification of a Stable ZnII–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O2 at Room Temperature

Identification of a Stable ZnII–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O2 at Room Temperature

Ab initiocalculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

Contact Info

Product

Resources

About

Ab initio Study of the Electronic Structure of Zinc Oxide and its Ions, ZnO^0,±. Ground and Excited States

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature

Identification of a Stable Zn^II–Oxyl Species Produced in an MFI Zeolite and Its Reversible Reactivity with O₂ at Room Temperature