Cryochemical studies. Part 8. Electron spin resonance spectra of dioxygen complexes of Group IB metal atoms

Howard, J. A.; Sutcliffe, R.; Mile, B.

doi:10.1021/j150663a032

Cited by 44 publications

(39 citation statements)

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“…The asymmetric local minimum of the lowest state, 'A", resulting from the SCF C,-symmetry optimization, leads to an energy slightly above that of the symmetric equilibrium geometry. This result is in agreement with some of the experimental data [20], but remains contrary to Illas et al's [23] theoretical findings.…”

Section: Resultssupporting

confidence: 78%

“…From these data, the presence of a nonsymmetric A,-0-0 species was inferred. Further experimental investigations by means of ESR techniques have also been reported where the spectroscopic data indicate a symmetric structure of silver dioxide possessing a side-on bonding with equivalent oxygen atoms [20]. More recently, Kasai and Jones [21], also based on matrix isolation ESR studies, have concluded that A , 0 2 presents a bent, end-on structure, thus again supporting the appearance of an asymmetric structure.…”

Section: Introductionmentioning

confidence: 88%

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A CI pseudopotential‐based description of the low‐lying states of A_g O₂

Bravo

Flores-Riveros

Novaro

1990

Int J of Quantum Chemistry

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Extensive SCF-LCAO-MO variational and perturbative configuration interaction (a) calculations framed within an effective core potential approximation have been performed to determine the two experimentally observed geometrical isomers of A g o z and the interconversion route between them. These structural forms, associated to the ground-state local minima, yield virtually the same energy, and their spontaneous interconversion is strongly indicated, which agrees fairly well with the experimental measurements. The reaction A, + Oz + Agoz was theoretically analyzed along a CI fully optimized energy pathway for the ground and various excited states, within Cz. and C, symmetry. Although a tight-ion pair (A: 0;) character is predicted for the ground state at the equilibrium geometries, its dissociation leads to neutral rather than to ionic fragments. The study of the reaction path within C, symmetry shows an avoided crossing between the ground state and another ' A" potential curve where the former correlates adiabatically with the reactants A,('S) + 02('Ag). This indicates that the formation of the complex proceeds via a reactive state of molecular oxygen. The higher ' A" electronic curves correlate with the metal ' P excited state, and the oxygen binding is found to be less favorable. The present results are shown to have an important bearing on the experimentally known catalytic properties of oxygen adsorbed on silver surfaces.

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Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 88%

A CI pseudopotential‐based description of the low‐lying states of A_g O₂

Bravo

Flores-Riveros

Novaro

1990

Int J of Quantum Chemistry

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“…[1][2][3][4][5][6] The observed vibrational frequencies provide the key evidence. Figure 3 shows a spectrum taken at 532 nm detachment wavelength ͑fluence: 40 mJ/cm 2 ͒ to enhance the spectral resolution for the 1.5 eV band.…”

mentioning

confidence: 87%

“…The interaction between Cu atom and O 2 is an important process and has been studied both in low temperature matrix [1][2][3][4][5][6] and in the gas phase. [7][8][9] Ground state Cu atom forms a molecular complex with O 2 , which takes on a bent CuOO ͑C s ͒ structure.…”

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confidence: 99%

Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

Desai

Wang

1995

The Journal of Chemical Physics

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Photoelectron spectroscopy of CuO−2 has been studied at three detachment wavelengths: 532 nm, 355 nm, and 266 nm. Vibrationally resolved spectra for two distinct isomers are observed: the Cu(O2) complex and the copper dioxide molecule. The Cu(O)2 complex has an electron affinity (EA) of 1.503 (10) eV with a ground state vibrational frequency of 530 (50) cm−1. Its first electronic excited state is 7400 (300) cm−1 above the ground state. The Cu(O2)− anion is also observed to undergo photodissociation to Cu−+O2 at both 532 nm and 355 nm detachment wavelengths. The copper dioxide molecule is found to have a high EA of 3.46 (4) eV. Three low-lying excited states are observed within 1 eV above the ground state. The first two excited states of the copper dioxide molecule both possess a totally symmetric vibrational frequency of 640 (60) cm−1.

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“…As said in the Introduction, EPR experiments [29][30][31] show two magnetically inequivalent oxygen atoms and this had been taken as an indication that the end-on Cs structure is the ground state. CASPT2 calculations by Roos et al 37 indicate that the gas-phase ground state is the side-on 2 A2 state but because of the small energy difference between the two species, the 2 A'' Cs structure, which has a large dipole moment, becomes the groundstate in rare-gas matrices.…”

Section: Tables 1-5 Herementioning

confidence: 97%

Structure, Bonding, and Relative Stability of the Ground and Low-Lying Electronic States of CuO₂. The Role of Exact Exchange

et al. 2009

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The C(2v) and C(s) ground and low-lying states of doublet CuO2 are examined for a series of different density functionals (pure, hybrid, and meta-hybrid) and CCSD(T) methods. The effect of changing the B3LYP functional a0 parameter is also explored. CCSD(T) results at the complete basis set limit show that the relative stability of the different electronic states is 2A(2)(C(2v)) < 2A''(Cs) < 2B(2)(C(2v)) < 2A'(C(s)) 2A(1)(C(2v)) < 2B(1)(C(2v)). Unlike CCSD(T), all DFT methods analyzed in this work erroneously predict the end-on 2A'' state as the ground state for CuO2 irrespective of the type of functional and percentage of Hartree-Fock (exact) exchange included in the B3LYP-like functional. Among the different functionals tested, B3LYP gives the best geometries and relative energies for the different electronic states when compared to CCSD(T) results. As for the effect of the a0 parameter, it is found that the B3LYP-like functional yielding better geometries contains 20% of exact exchange, although somewhat unexpectedly, the B3LYP-like functional with a larger contribution of exact exchange (90%) is the one that gives the smaller standard deviation for relative energies.

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Cryochemical studies. Part 8. Electron spin resonance spectra of dioxygen complexes of Group IB metal atoms

Cited by 44 publications

References 0 publications

A CI pseudopotential‐based description of the low‐lying states of A_g O₂

A CI pseudopotential‐based description of the low‐lying states of A_g O₂

Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

Structure, Bonding, and Relative Stability of the Ground and Low-Lying Electronic States of CuO₂. The Role of Exact Exchange

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Cryochemical studies. Part 8. Electron spin resonance spectra of dioxygen complexes of Group IB metal atoms

Cited by 44 publications

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A CI pseudopotential‐based description of the low‐lying states of Ag O2

A CI pseudopotential‐based description of the low‐lying states of Ag O2

Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

Structure, Bonding, and Relative Stability of the Ground and Low-Lying Electronic States of CuO2. The Role of Exact Exchange

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A CI pseudopotential‐based description of the low‐lying states of A_g O₂

A CI pseudopotential‐based description of the low‐lying states of A_g O₂

Structure, Bonding, and Relative Stability of the Ground and Low-Lying Electronic States of CuO₂. The Role of Exact Exchange