Kinetics of Aminocarbyne Formation on Pt(111)

Hu, Xiaofeng; Yin, Jun; Meyer, Randall J.; Trenary, Michael

doi:10.1021/jp507026k

Cited by 3 publications

(2 citation statements)

References 31 publications

(52 reference statements)

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“…A variety of reaction types, including molecular and dissociative adsorptions, desorptions, and bimolecular and unimolecular reactions, are covered in this set. Most of these reactions have been investigated previously using the NEB method by other researchers . In summary, 43 elementary reactions which consists of nine different metals, one metal oxide, and seven different surface terminations were studied.…”

Section: Methodsmentioning

confidence: 99%

“…Most of these reactions have been investigated previously using the NEB method by other researchers. [120][121][122][123][124][125][126][127][128][129][130][131][132][133][134][135] In summary, 43 elementary reactions which consists of nine different metals, one metal oxide, and seven different surface terminations were studied. Summaries of the reactions are given in Table 1.…”

Section: Surface Reaction Validation Test Setmentioning

confidence: 99%

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Reliable and efficient reaction path and transition state finding for surface reactions with the growing string method

Jafari

Zimmerman

2017

J Comput Chem

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The computational challenge of fast and reliable transition state and reaction path optimization requires new methodological strategies to maintain low cost, high accuracy, and systematic searching capabilities. The growing string method using internal coordinates has proven to be highly effective for the study of molecular, gas phase reactions, but difficulties in choosing a suitable coordinate system for periodic systems has prevented its use for surface chemistry. New developments are therefore needed, and presented herein, to handle surface reactions which include atoms with large coordination numbers that cannot be treated using standard internal coordinates. The double-ended and single-ended growing string methods are implemented using a hybrid coordinate system, then benchmarked for a test set of 43 elementary reactions occurring on surfaces. These results show that the growing string method is at least 45% faster than the widely used climbing image-nudged elastic band method, which also fails to converge in several of the test cases. Additionally, the surface growing string method has a unique single-ended search method which can move outward from an initial structure to find the intermediates, transition states, and reaction paths simultaneously. This powerful explorative feature of single ended-growing string method is demonstrated to uncover, for the first time, the mechanism for atomic layer deposition of TiN on Cu(111) surface. This reaction is found to proceed through multiple hydrogen-transfer and ligand-exchange events, while formation of H-bonds stabilizes intermediates of the reaction. Purging gaseous products out of the reaction environment is the driving force for these reactions. © 2017 Wiley Periodicals, Inc.

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Section: Methodsmentioning

confidence: 99%

Section: Surface Reaction Validation Test Setmentioning

confidence: 99%

Reliable and efficient reaction path and transition state finding for surface reactions with the growing string method

Jafari

Zimmerman

2017

J Comput Chem

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Theoretical study of the H + HCN → H + HNC process

et al. 2017

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We present a theoretical study on the detailed mechanism and kinetics of the H + HCN → H + HNC process. The potential energy surface was calculated at the complete basis set quantum chemical method, CBS-QB3. The vibrational frequencies and geometries for four isomers (H CN, cis-HCNH, trans-HCNH, CNH), and seven saddle points (TSn where n = 1 - 7) are very important and must be considered during the process of formation of the HNC in the reaction were calculated at the B3LYP/6-311G(2d,d,p) level, within CBS-QB3 method. Three different pathways (PW1, PW2, and PW3) were analyzed and the results from the potential energy surface calculations were used to solve the master equation. The results were employed to calculate the thermal rate constant and pathways branching ratio of the title reaction over the temperature range of 300 up to 3000 K. The rate constants for reaction H + HCN → H + HNC were fitted by the modified Arrhenius expressions. Our calculations indicate that the formation of the HNC preferentially occurs via formation of cis-HCNH, the fitted expression is k (T) = 9.98 × 10 T exp(-7.62 kcal.mol/R T) while the predicted overall rate constant k (T) = 9.45 × 10 T exp(-8.56 kcal.mol/R T) in cm molecule s . Graphical Abstract (a) Potential energy surface, (b) thermal rate constants as a function of temperature and

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