Structures and vibrational frequencies of FOOF and FONO using density functional theory

Amos, Roger D.; Murray, Christopher W.; Handy, Nicholas C.

doi:10.1016/0009-2614(93)90036-z

Cited by 33 publications

(16 citation statements)

References 31 publications

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“…21 The use of cc-pVmZ basis sets, however, deteriorates the performance of DFT irrespective of the functional used so that the LDA results of Table 2 cannot compete with results of previous investigations based on HF-optimized basis sets (Table 5). 21,22 Similarly as for the MP2 and CCSD(T) description of 1, we find that for certain compositions of the basis set a fortuitously accurate geometry of 1 is obtained; however, if standard correlation consistent basis sets are stepwise increased to reach the CBS limit at DFT, the resulting geometry will be less accurate than the CCSD(T)/CBS limit geometry obtained with the aug-cc-pVmZ basis sets. This holds for all functionals applied in this work where the B3LYP functional performs better than both the BLYP and mPW1PW91 functionals.…”

Section: Ccsd(t) Geometriesmentioning

confidence: 90%

Quantum Chemical Descriptions of FOOF: The Unsolved Problem of Predicting Its Equilibrium Geometry

Kraka

2001

J. Phys. Chem. A

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Single determinant Møller-Plesset perturbation (MP) theory at second order (MP2), third order (MP3), and fourth order (MP4) with standard basis sets ranging from cc-pVDZ to cc-pVQZ quality predicts the equilibrium geometry of FOOF qualitatively incorrect. Sixth-order MP (MP6), CCSD(T), and DFT lead to a qualitatively correct FOOF equilibrium geometry r e , provided a sufficiently large basis set is used; however, even these methods do not succeed in reproducing an exact r e geometry. The latter can be achieved only by artificially increasing anomeric delocalization of electron lone pairs at the O atoms into the σ*(OF) orbitals by selectively adding diffuse basis functions, adjusting exponents of polarization functions, or enforcing an increase of electron pair correlation effects via the choice of a rigid basis set. DFT geometries of FOOF can be improved in a similar way and, then, DFT presents the best cost-efficiency compromise currently available for describing FOOF and related molecules. DFT and CCSD(T) calculations reveal that FOOF can undergo either rotation at the OO bond or dissociation into FOO and F because the corresponding barriers (trans barrier: 19.4 kcal/ mol; dissociation barrier 19.5 kcal/mol) are comparable. Previous estimates as to the height of the rotational barriers of FOOF are largely exaggerated. Rotation at the OO bond raises the barrier to dissociation because the anomeric effect is switched off. The molecular dipole moment is found to be a sensitive antenna for probing the quality of the quantum chemical description of FOOF.

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Section: Ccsd(t) Geometriesmentioning

confidence: 90%

Quantum Chemical Descriptions of FOOF: The Unsolved Problem of Predicting Its Equilibrium Geometry

Kraka

2001

J. Phys. Chem. A

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“…The fluorine peroxide molecule is well known to be a very difficult problem [32][33][34][35][36][37][38][39] for standard ab initio method. While barriers have not been experimentally measured, they are expected to be higher than those of hydrogen peroxide.…”

Section: Fluorine Peroxide F 2 Omentioning

confidence: 99%

A Quest for the Origin of Barrier to the Internal Rotation ofHydrogen Peroxide (H2O2) and Fluorine Peroxide (F2O2)

Ghosh

2006

IJMS

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Abstract:In order to understand the structure-property relationship, SPR, an energypartitioning quest for the origin of the barrier to the internal rotation of two iso-structural molecules, hydrogen peroxide, H 2 O 2 , and fluorine peroxide, F 2 O 2 is performed. The hydrogen peroxide is an important bio-oxidative compound generated in the body cells to fight infections and is an essential ingredient of our immune system. The fluorine peroxide is its analogue. We have tried to discern the interactions and energetic effects that entail the nonplanar skew conformation as the equilibrium shape of the molecules. The physical process of the dynamics of internal rotation initiates the isomerization reaction and generates infinite number of conformations. The decomposed energy components faithfully display the physical process of skewing and eclipsing as a function of torsional angles and hence are good descriptors of the process of isomerization reaction of hydrogen peroxide (H 2 O 2 ) and dioxygen difluoride (F 2 O 2 ) associated with the dynamics of internal rotation. It is observed that the one-center, two-center bonded and nonbonded interaction terms are sharply divided in two groups. One group of interactions hinders the skewing and favours planar cis/trans forms while the other group favours skewing and prefers the gauche conformation of the molecule. The principal energetic effect forcing the molecules into the nonplanar gauche form is the variation "O-O' bond energy with torsion in both the molecules. It is demonstrated that the barrier is not a regional effect rather it is made by the conjoint action of all one-and two-center bonding and nonbonding interactions comprising the entire framework of the molecule. The present study claims to reveal one amazing feature of nonbonded interactions. Computed results of nonbonding interactions demonstrate that the nature of interaction between two formally positively charged non-bonding H atoms (H δ+ ----

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“…[106] B3LYP/6-311 + +G(2d,2p) results are off by more than AE 0.05 . [107] None of the DFT calculations reported by Jursic [109,110] using different functionals (SVWN, BECKE3LYP, BECKE3P86, BLYP, BP86) with 6-311 + + G(2d) basis sets reproduces the two bond lengths better than AE 0.02 . B3LYP and PBE methods with cc-pVDZ to cc-pVQZ basis sets do not produce satisfactory results.…”

Section: Fo-ofmentioning

confidence: 98%

“…For more than 30 years a large number of calculations using almost every quantum chemical ab initio method available, such as HF, MP2, MP3, MP4, CISD, QCISD, CEPA, CCSD, CCSD(T), QCISD(T), CASSCF and CCI, as well as DFT methods were reported. [93,[98][99][100][101][102][103][104][105][106][107][108][109][110][111][112][113][114][115][116] A summary of calculations performed before the year 2000 is given by Kraka and Cremer. [112] Most of these calculations fail strongly to reproduce the experimental geometry and Schaefer called this molecule a "nightmare for theoreticians".…”

Section: Fo-ofmentioning

confidence: 99%

“…[112] In addition to these ab initio calculations a large number (about 100) of density functional theory calculations (DFT) were performed, using different functionals and basis sets. [105][106][107][108][109][110][113][114][115] In general, the structure of difluorine dioxide is reproduced better by DFT methods than by ab initio calculations. With the LDF method and TZ and QZ basis sets Dixon et al predict both bond lengths better than AE 0.02 .…”

Section: Fo-ofmentioning

confidence: 99%

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Gas Phase Structures of Peroxides: Experiments and Computational Problems

Oberhammer

2014

ChemPhysChem

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Gas-phase structures of several organic and inorganic peroxides X-O-O-X and X-O-O-X', which have been determined experimentally by gas electron diffraction and/or microwave spectroscopy, are discussed. The OO bond length in these peroxides varies from 1.481(8) Å in Me3 SiOOSiMe3 to 1.214(2) Å in FOOF and the dihedral angle ϕ(XO-OX) between 0° in HC(O)O-OH and near 180° in Bu(t) O-OBu(t) . Some of the peroxides cause problems for quantum chemistry, since several computational methods fail to reproduce the experimental structures. Extreme examples are MeO-OMe and FO-OF. In the case of MeO-OMe only about half of the more than 100 computational methods reported in the literature reproduce the experimentally determined double-minimum shape of the torsional potential around the OO bond correctly. For FO-OF only a small number of close to 200 computational methods reproduce the OO and OF bond lengths better than ±0.02 Å.

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Structures and vibrational frequencies of FOOF and FONO using density functional theory

Cited by 33 publications

References 31 publications

Quantum Chemical Descriptions of FOOF: The Unsolved Problem of Predicting Its Equilibrium Geometry

Quantum Chemical Descriptions of FOOF: The Unsolved Problem of Predicting Its Equilibrium Geometry

A Quest for the Origin of Barrier to the Internal Rotation ofHydrogen Peroxide (H2O2) and Fluorine Peroxide (F2O2)

Gas Phase Structures of Peroxides: Experiments and Computational Problems

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