Addition of Atoms to Olefins in the Gas Phase

Cvetanović, R. J.

doi:10.1002/9780470133316.ch5

Cited by 210 publications

(32 citation statements)

References 93 publications

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“…As reported, the oxene species can add to conjugated carbon-carbon unsaturated bond, but the intermediate of the reaction can easily polymerize and yield a resinous product. If such polymerization does not occur, the main products should be phenol that results from the neighbor insert hydrogen (NIH) shift [25,26]. In the reported mechanism, the main products were 3-hydroxyl-cyclohexene.…”

Section: Resultsmentioning

confidence: 93%

Heterogeneous hydroxylation catalyzed by multi-walled carbon nanotubes at low temperature

Kang

Wang

Mao

et al. 2006

Applied Catalysis A: General

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Section: Resultsmentioning

confidence: 93%

Heterogeneous hydroxylation catalyzed by multi-walled carbon nanotubes at low temperature

Kang

Wang

Mao

et al. 2006

Applied Catalysis A: General

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“…Transform the appropriate spin blocks (see Appendix) of the DM into the AO basis; combine the transformed blocks to form the Cartesian components of the DM. 4. Contract the x, y, and z SOC integrals with the respective density matrices to yield the real and imaginary components of the SOC:…”

Section: E Implementationmentioning

confidence: 99%

“…Further approximations such as used in the AMFI approach introduce only minor errors. 4. The basis-set dependence of the SOCs in these species has been extensively investigated in Ref.…”

Section: The Differences Between the Full Two-electron Treatment Andmentioning

confidence: 99%

“…Although small in absolute magnitude (typical values of SOCs in organic molecules vary from several to hundreds of wave numbers), SOC facilitates the mixing of otherwise non-interacting states (e.g., singlet and triplet states); thus, it opens up new relaxation pathways for electronically excited states (via inter-system crossing, ISC) and enables new reaction channels. [1][2][3] For example, the reactions of O( 3 P) or O 2 ( 3 Σ − g ) with unsaturated hydrocarbons, which are common in combustion, proceed through triplet diradical formation [4][5][6][7][8][9][10][11][12][13][14][15] and the closed-shell singlet products can only be formed through ISC. Other examples of spin-forbidden processes in molecules composed of light elements involve reactions of N( 4 S) and O( 1 D).…”

Section: Introductionmentioning

confidence: 99%

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Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations

Epifanovsky

Klein

Stopkowicz

et al. 2015

The Journal of Chemical Physics

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We present a formalism and an implementation for calculating spin-orbit couplings (SOCs) within the EOM-CCSD (equation-of-motion coupled-cluster with single and double substitutions) approach. The following variants of EOM-CCSD are considered: EOM-CCSD for excitation energies (EOM-EE-CCSD), EOM-CCSD with spin-flip (EOM-SF-CCSD), EOM-CCSD for ionization potentials (EOM-IP-CCSD) and electron attachment (EOM-EA-CCSD). We employ a perturbative approach in which the SOCs are computed as matrix elements of the respective part of the Breit-Pauli Hamiltonian using zeroth-order non-relativistic wave functions. We follow the expectation-value approach rather than the response-theory formulation for property calculations. Both the full two-electron treatment and the mean-field approximation (a partial account of the two-electron contributions) have been implemented and benchmarked using several small molecules containing elements up to the fourth row of the periodic table. The benchmark results show the excellent performance of the perturbative treatment and the mean-field approximation. When used with an appropriate basis set, the errors with respect to experiment are below 5% for the considered examples. The findings regarding basis-set requirements are in agreement with previous studies. The impact of different correlation treatment in zeroth-order wave functions is analyzed. Overall, the EOM-IP-CCSD, EOM-EA-CCSD, EOM-EE-CCSD, and EOM-SF-CCSD wave functions yield SOCs that agree well with each other (and with the experimental values when available). Using an EOM-CCSD approach that provides a more balanced description of the target states yields more accurate results.

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“…The reactions of triplet state oxygen atoms with the unsaturated hydrocarbons ethylene and acetylene provide a number of interesting comparisons and contrasts. 1 In the ethylene case, the initially formed oxirane diradical generated by C-O bond formation first undergoes rapid intersystem crossing, following which either hydrogen atom emission to form the vinyloxy radical or C-C bond cleavage to form CH 3 + HCO occurs. In contrast, the reaction with acetylene, which also involves incipient C-O bond formation and competition between H-atom emission or C-C bond cleavage, appears to take place entirely on the triplet surface.…”

Section: Introductionmentioning

confidence: 99%

Reaction dynamics of OH+(Σ−3)+C2H2 studied with crossed beams and density functional theory calculations

Liu

Martin

Farrar

2006

The Journal of Chemical Physics

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The reactions between OH+(3Sigma-) and C2H2 have been studied using crossed ion and molecular beams and density functional theory calculations. Both charge transfer and proton transfer channels are observed. Products formed by carbon-carbon bond cleavage analogous to those formed in the isoelectronic O(3P)+C2H2 reaction, e.g., 3CH2 + HCO+, are not observed. The center of mass flux distributions of both product ions at three different energies are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The internal energy distributions of the charge transfer products are independent of collision energy and are peaked at the reaction exothermicity, inconsistent with either the existence of favorable Franck-Condon factors or energy resonance. In proton transfer, almost the entire reaction exothermicity is transformed into product internal excitation, consistent with mixed energy release in which the proton is transferred with both the breaking and forming bonds extended. Most of the incremental translational energy in the two higher-energy experiments appears in product translational energy, providing an example of induced repulsive energy release.

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Addition of Atoms to Olefins in the Gas Phase

Cited by 210 publications

References 93 publications

Heterogeneous hydroxylation catalyzed by multi-walled carbon nanotubes at low temperature

Heterogeneous hydroxylation catalyzed by multi-walled carbon nanotubes at low temperature

Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations

Reaction dynamics of OH+(Σ−3)+C2H2 studied with crossed beams and density functional theory calculations

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