Full-dimensional automated potential energy surface development and detailed dynamics for the CH₂OO + NH₃ reaction

Abstract

With the help of ROBOSURFER program package, a global full-dimensional potential energy surface (PES) for the reaction of the Criegee intermediate, CH2OO, with the NH3 molecule is developed iteratively using...

First-principles mode-specific reaction dynamics

“…Espinosa-Garcı ´a and coworkers 77,78 and/or our group 90,91,93 investigated the modespecificity in the reactions of ethane (C 2 H 6 ) with H, F, Cl, and OH, while Lu and Li 82 studied the F + CH 3 OH reaction. We also reported mode-specific computations for HBr/HI + C 2 H 5 , [96][97][98] CH 2 OO + NH 3 99 and post-six-atomic ion-molecule reactions, such as OH À + CH 3 I 102 and F À + CH 3 CH 2 Cl. 54 In the present Perspective article, we focus on our most recent first-principles mode-specific dynamics studies of the F/Cl/OH + C 2 H 6 , 90,91,93 HBr/HI + C 2 H 5 , 96-98 OH À + CH 3 I, 102 and F À + CH 3 CH 2 Cl 54 reactions, covering both neutral and ionic systems with 7-10 atoms.…”

“…We applied the QCT method for several mode-specific studies on post-six-atom reactions 54,90,91,93,[96][97][98][99]102 and below we highlight our representative results. Fig.…”

“…65–102 Espinosa-García and co-workers 77,78 and/or our group 90,91,93 investigated the mode-specificity in the reactions of ethane (C 2 H 6 ) with H, F, Cl, and OH, while Lu and Li 82 studied the F + CH 3 OH reaction. We also reported mode-specific computations for HBr/HI + C 2 H 5 , 96–98 CH 2 OO + NH 3 99 and post-six-atomic ion–molecule reactions, such as OH − + CH 3 I 102 and F − + CH 3 CH 2 Cl. 54…”

Dynamics of the HCl + C2H5 Multichannel Reaction on a Full-Dimensional Ab Initio Potential Energy Surface

“…The theoretical dynamical investigation of systems containing more than six atoms on full-dimensional analytical potential energy surfaces (PESs) has only become feasible in the recent decade(s). − Following the extensive literature on atom + H 2 O/CH 4 reactions, − the atom + C 2 H 6 reactions have emerged as the new benchmark systems, − which represent several new possibilities and also many challenges for reaction dynamics studies: (1) rules of thumb discovered for small/medium-sized reactions can be extended for polyatomic reactivity, (2) these reactions often involve multiple competitive reaction channels, calling for sophisticated PES development techniques, and (3) with the increasing number of degrees of freedom, mode- and bond-selectivity are of major interest in these complex systems. Many of such investigations have enriched our knowledge in recent years, using quasi-classical trajectory (QCT) computations.…”

“…Following initial QCT studies of atom + ethane reactions on force-field-based PESs, , high-quality ab initio potential energy surfaces have been developed by our group for different reactions of ethane, using an automated improvement strategy, providing excellent agreement with dynamics experiments regarding the HF/HCl product rotational and/or vibrational distributions for the F and Cl + C 2 H 6 reactions, , and mode-specific vibrational populations of H 2 O in the OH + ethane reaction . Other polyatomic reactions, such as O­( 3 P) + C 2 H 4 , OH + CH 4 , H/F/Cl/OH + CH 3 OH, − OH – + CH 3 F/CH 3 I, ,, F – (H 2 O)/Cl – (H 2 O) + CH 3 I, Cl + propene/pentane, , F – /OH – + CH 3 CH 2 Cl, , NH 2 – + CH 3 I, HBr/HI + C 2 H 5 , , H 2 O/NH 3 + CH 2 OO, , F/Cl + CH 3 NH 2 , , and F – + (CH 3 ) 3 CI, have also been the subjects of QCT simulations, and vibrational and rotational mode-specificity have been explored in several of these postsix-atomic systems. Additionally, reduced-dimensional quantum dynamics computations have also been performed for such polyatomic reactions. − …”