Recent advances in quantum scattering calculations on polyatomic bimolecular reactions

Abstract

This review surveys quantum scattering calculations on chemical reactions of polyatomic molecules in the gas phase published in the last ten years. These calculations are useful because they provide highly accurate information on the dynamics of chemical reactions which can be compared in detail with experimental results. They also serve as quantum mechanical benchmarks for testing approximate theories which can more readily be applied to more complicated reactions. This review includes theories for calculating quantities such as rate constants which have many important scientific applications.

Heavy‐Atom Tunneling in Organic Reactions

“…Annulene p-BS dominated by tunneling is not, however, limited to automerization via planar or nearly planar transition states.F acile thermal cis/trans isomerization (configuration change) in medium-and large-sized annulenes is awell-known phenomenon. [25,28] Prior computational work by our group invoked both Mçbius aromatic and antiaromatic p-BS transition states to rationalize this rapid reaction for [12]-, [14]-and [16]annulenes. [29] Fore xample,i n [ 16]annulene, thermal cis/trans isomerization interconverting 7a and 8a (observed by NMR [25] ), has an experimental E a of 10.25 kcal mol À1 (À508 8 C).…”

Stereodynamical control of product branching in multi-channel barrierless hydrogen abstraction of CH3OH by F

“…[2][3][4][5][6][7] Recent focus has been shied to more complex ones, such as the H/F/Cl/O/OH + CH 4 (the simplest hydrocarbon) reactions. [8][9][10][11] These studies have played a pivotal role in advancing our understanding of fundamental mechanisms and dynamics in chemical reactions, and have shed valuable light on a wide array of important dynamical issues such as tunneling, resonance, mode specicity and bond selectivity, steric effects, and nonadiabatic effects.…”

When Classical Trajectories Get to Quantum Accuracy: The Scattering of H2on Pd(111)

“…[1][2][3][4][5][6][7][8][9][10] For chemical reactions involving a small number of degrees-of-freedom (DOF) (typically less than or equal to 6), quantum dynamics calculations might be now regarded as exact since they generally provide results in excellent agreement with experiments. 11,12 However, reaction dynamics studies focus on systems of ever increasing size [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] for which the quasi-classical trajectory (QCT) method is at this time the only practical tool to apply. A crucial issue is thus to develop theoretically justified corrections to carry out classical dynamics studies of chemical reactions in a quantum spirit.…”