Manipulating tunnelling gateways in condensed phase isomerization

• الحاوية / القاعدة: Natural Sciences
• المؤلفون الرئيسيون: Arnab Choudhury, Shreya Sinha, David Harlander, Jessalyn DeVine, Alexander Kandratsenka, Peter Saalfrank, Dirk Schwarzer, Alec M. Wodtke
• التنسيق: مقال
• اللغة: الإنجليزية
• منشور في: Wiley-VCH 2023-07-01
• الموضوعات: astrochemistry; gateway tunneling; isomerization; tunneling
• الوصول للمادة أونلاين: https://doi.org/10.1002/ntls.20230006

Abstract When a chemical reaction occurs via tunnelling, a simple mass‐dependence is expected, where substitution of atoms by heavier isotopes leads to a reduced reaction rate. However, as shown in a recent study of CO orientational isomerization at the NaCl(1 0 0) interface, the lightest isotopologues need not exhibit the fastest tunnelling; for the CO/NaCl system, the non‐monotonic mass‐dependence is understood through a new picture of condensed phase tunnelling where the overall rate is dominated by a few pairs of reactant/product states. These state‐pairs – termed quantum gateways – gain dynamical importance through accidentally enhanced tunnelling probabilities, facilitated by a confluence of the energetic landscape underlying the reaction as well as the phonon bath of the surrounding medium. Here, we explore gateway tunnelling through measurements of the kinetic isotope effect for CO isomerization in a monolayer buried by many layers of either CO or N2. With an N2 overlayer, tunnelling rates are accelerated for all four isotopologues (12C16O, 13C16O, 12C18O and 13C18O), but the degree of acceleration is isotopologue‐specific and non‐intuitively mass dependent. A one‐dimensional tunnelling model involving an Eckart barrier cannot capture this behaviour. This reflects how a modification of the potential energy surface moves states in and out of resonance, thereby changing which tunnelling gateways can be accessed in the isomerization reaction. Key points The paper describes new systems that showcase resonance‐enhanced condensed phase tunnelling. Condensed phase tunnelling as described in this work may have implications for astrochemistry. A previously hypothesized mechanism is subjected to subsequent experimental scrutiny – the hypothesis stands the test.