Locating the rate-limiting step for the interaction of hydrogen withMg(0001)using density-functional theory calculations and rate theory

Understanding the mechanism of the catalytic upgrade of bio-oils via the process of hydrodeoxygenation (HDO) is desirable to produce targeted oxygen-deficient bio-fuels. We have used calculations based on the density functional theory to investigate the reaction mechanism of HDO of guaiacol over Cu (111) surface in the presence of H2, leading to the formation of catechol and anisole. Our analysis of the thermodynamics and kinetics involved in the reaction process shows that catechol is produced via direct demethylation, followed by dehydrogenation of –OH and re-hydrogenation of catecholate in a concerted fashion. The de-methylation step is found to be the rate-limiting step for catechol production with a barrier of 1.97 eV. Formation of anisole will also proceed via the direct dehydroxylation of guaiacol followed by hydrogenation. Here, the rate-limiting step is the dehydroxylation step with an energy barrier of 2.07 eV. Thermodynamically, catechol formation is favored while anisole formation is not favored due to the weaker interaction seen between anisole and the Cu (111) surface, where the binding energies of guaiacol, catechol, and anisole are -1.90 eV, −2.18 eV, and −0.72 eV, respectively. The stepwise barriers also show that the Cu (111) surface favors catechol formation over anisole as the rate-limiting barrier is higher for anisole production. For catechol, the overall reaction is downhill, implying that this reaction path is thermodynamically and kinetically preferred and that anisole, if formed, will more easily transform.

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Ab Initio and Density Functional Theory Evidence on the Rate-Limiting Step in the Morita−Baylis−Hillman Reaction

Organic Letters ◽

10.1021/ol801540x ◽

2008 ◽

Vol 10 (16) ◽

pp. 3651-3651

Author(s):

Dipankar Roy ◽

Raghavan B. Sunoj

Keyword(s):

Density Functional Theory ◽

Ab Initio ◽

Density Functional ◽

Functional Theory ◽

Rate Limiting Step ◽

Limiting Step ◽

Rate Limiting

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Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

Science ◽

10.1126/science.abd8408 ◽

2021 ◽

Vol 372 (6544) ◽

pp. 847-852

Author(s):

Qiaomu Yang ◽

Yu-Heng Wang ◽

Yusen Qiao ◽

Michael Gau ◽

Patrick J. Carroll ◽

...

Keyword(s):

Density Functional ◽

Fossil Fuels ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Radical Trapping ◽

Rate Limiting Step ◽

Photocatalytic System ◽

Step Density ◽

Rate Limiting

The functionalization of methane, ethane, and other alkanes derived from fossil fuels is a central goal in the chemical enterprise. Recently, a photocatalytic system comprising [CeIVCl5(OR)]2− [CeIV, cerium(IV); OR, –OCH3 or –OCCl2CH3] was disclosed. The system was reportedly capable of alkane activation by alkoxy radicals (RO•) formed by CeIV–OR bond photolysis. In this work, we present evidence that the reported carbon-hydrogen (C–H) activation of alkanes is instead mediated by the photocatalyst [NEt4]2[CeCl6] (NEt4+, tetraethylammonium), and RO• are not intermediates. Spectroscopic analyses and kinetics were investigated for C–H activation to identify chlorine radical (Cl•) generation as the rate-limiting step. Density functional theory calculations support the formation of [Cl•][alcohol] adducts when alcohols are present, which can manifest a masked RO• character. This result serves as an important cautionary note for interpretation of radical trapping experiments.

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THEORETICAL INVESTIGATION ON THE ACTIVATION OF ETHANE VIA NICKEL ATOM CATALYSIS

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633607002976 ◽

2007 ◽

Vol 06 (02) ◽

pp. 323-330 ◽

Cited By ~ 2

Author(s):

LAI-CAI LI ◽

JUN-LING LIU ◽

JING SHANG ◽

XIN WANG ◽

NING-BEW WONG

Keyword(s):

Density Functional ◽

Bond Activation ◽

Theoretical Work ◽

Nickel Atom ◽

Functional Theory ◽

Activation Pathway ◽

Rate Determining Step ◽

Rate Limiting Step ◽

Limiting Step ◽

Rate Limiting

The reaction mechanism of the activation of ethane by nickel atom has been investigated by density functional theory (DFT). The geometries and vibration frequencies of reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311 + +G(d, p) level. Two main pathways, C – C bond activation and C – H bond activation, are identified. In former channel, the rate-limiting step is found to be hydrogen-transferring step with a high barrier of 227 kJ · mol-1. In the C – H bond activation pathway, the second hydrogen-transferring step is the rate-determining step of the whole reaction. The barrier of the step is 71 kJ · mol-1. Our results show that the studied reaction would undergo along C – H bond activation pathway to form the products H 2 molecule and Ni ⋯ethene complex. The present theoretical work indicates that Ni atom is more active than Ni + cation in activating ethane.

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Boron Diffusion Mechanism in Silicon Oxide Using AB Initio Methods

MRS Proceedings ◽

10.1557/proc-610-b5.11 ◽

2000 ◽

Vol 610 ◽

Cited By ~ 4

Author(s):

V. Zubkov ◽

J. P. Senosiain ◽

S. Aronowitz ◽

V. Sukharev ◽

C. B. Musgrave

Keyword(s):

Density Functional ◽

Silicon Oxide ◽

Diffusion Mechanism ◽

Activation Energies ◽

Boron Diffusion ◽

Functional Theory ◽

Model Cluster ◽

Rate Limiting Step ◽

Limiting Step ◽

Rate Limiting

AbstractDensity functional theory was employed to explore the diffusion mechanism of boron in amorphous silicon oxide. The oxide was modeled with clusters of various sizes, and both neutral boron atoms and cations were considered. Three stable structures were found where B (or B+) was inserted into oxide: one in which B (or B+) is divalent and two in which B (or B+) is trivalent. Boron diffusion through silicon oxide proceeds as a sequence of B hops from one inserted position to another. For neutral boron the rate limiting step is B hop from one of trivalent structures to a divalent one with activation energies (Ea) in the range of 2.0-3.1 eV, depending on the model cluster. In the case of a cation the rate-limiting step is the B+ hop over the O atom in a divalent structure Si-B+-O-Si with calculated Ea of 2.4-2.8 eV. Experimental activation energies for B diffusion in silicon oxide are in the 2.3 - 4.2 eV range. Our results suggest that both neutral and cation boron can participate in B diffusion in oxide.

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A Joint Study on Juglone Metal Complexes by InfraredÂ Spectroscopy and Density Functional Theory Calculations

10.3390/ecsoc-17-e005 ◽

2013 ◽

Author(s):

Ines Mancini ◽

Andrea Defant ◽

Costantino Tomasi

Keyword(s):

Density Functional Theory ◽

Metal Complexes ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Joint Study

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Is a Non-Transition Element Nitride Ferromagnet Ever Achievable? Indication of the N-N Pairing Instability

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20061525 ◽

2006 ◽

Vol 71 (11-12) ◽

pp. 1525-1531 ◽

Cited By ~ 3

Author(s):

Wojciech Grochala

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Transition Element ◽

Density Functional Theory Calculations ◽

Functional Theory

The enthalpy of four polymorphs of CaN has been scrutinized at 0 and 100 GPa using density functional theory calculations. It is shown that structures of diamagnetic calcium diazenide (Ca2N2) are preferred over the cubic ferromagnetic polymorph (CaN) postulated before, both at 0 and 100 GPa.

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Tensor-structured algorithm for reduced-order scaling large-scale Kohn–Sham density functional theory calculations

npj Computational Materials ◽

10.1038/s41524-021-00517-5 ◽

2021 ◽

Vol 7 (1) ◽

Author(s):

Chih-Chuen Lin ◽

Phani Motamarri ◽

Vikram Gavini

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Large Scale ◽

Density Functional Theory Calculations ◽

System Size ◽

Real Space ◽

Functional Theory ◽

Reduced Order ◽

Separable Approximation ◽

Tensor Basis

AbstractWe present a tensor-structured algorithm for efficient large-scale density functional theory (DFT) calculations by constructing a Tucker tensor basis that is adapted to the Kohn–Sham Hamiltonian and localized in real-space. The proposed approach uses an additive separable approximation to the Kohn–Sham Hamiltonian and an L1 localization technique to generate the 1-D localized functions that constitute the Tucker tensor basis. Numerical results show that the resulting Tucker tensor basis exhibits exponential convergence in the ground-state energy with increasing Tucker rank. Further, the proposed tensor-structured algorithm demonstrated sub-quadratic scaling with system-size for both systems with and without a gap, and involving many thousands of atoms. This reduced-order scaling has also resulted in the proposed approach outperforming plane-wave DFT implementation for systems beyond 2000 electrons.

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