Dynamics of carbon monoxide dissociation on Co(112̄0)

Abstract

The dissociative chemisorption dynamics of CO on rigid Co(112[combining macron]0) is investigated using a quasi-classical trajectory method on a new global six-dimensional potential energy surface (PES). The PES is fit using a neural network method to represent 24 630 density functional energies in various configurations. The reaction path features deep chemisorption wells and a late barrier for dissociation, agreeing well with previous calculations. The activation energy for dissociation ranges from 0.1 eV at the hollow site to 2.46 eV on the top site, indicating a highly corrugated PES. Effects of the incidence energy of the impinging molecule, its initial orientation, vibrational and rotational excitations, and site specificity are examined. Despite the presence of a low barrier, the initial dissociation probability is very small, even at high incident energies, as a large percentage of trajectories is either trapped or desorbed back to the gas phase. The low reactivity is attributed to inefficient energy transfer into the dissociation reaction coordinate in the chemisorption well where thermal equilibrium is not reached. This system underscores the importance of dynamics in understanding reactions at gas-surface interfaces and in kinetic modeling of catalytic processes.

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

“…101,[143][144][145][146][147][148][149][150][151] Researchers are also starting to use meta-GGA (mGGA) DFs. 151,152 Goals of these calculations include validating models, 61,62,65,73,74,76,86,89,98,100,102,105,106,123,145,153 analyzing features of the reaction mechanism, 21,51,53,58,[64][65][66][69][70][71][72]75,77,[79][80][81][82]87,[90][91][92][93][94]…”

Quantum Effects in the Dissociative Chemisorption of N2 on Fe(111): Full-Dimensional Quantum Dynamics and Quasi-Classical Trajectory Study

“…The interaction between gas-phase molecules and the transition-metal surface plays an important role in heterogeneous catalysis, − for example, the famous industrial catalytic reactionthe synthesis of ammonia from N 2 and H 2 over an iron-based catalysis. In this ammonia synthesis process, the dissociative chemisorption (DC) of the N 2 molecule is the rate-limiting step. , Iron is a well-known and efficient catalyst for ammonia synthesis, mainly because of its low price and high reactivity.…”

Vibrational enhancement in the dynamics of ammonia dissociative chemisorption on Ru(0001)

“…The "early stop" method was used to avoid overfitting. Following our previous work, [29,52] a primitive PES was first fit with the points extracted from ~2000 AIMD trajectories. Once the primitive 6 PES was constructed, more points were sampled by QCT calculations.…”