Atom-Tunneling in Chemistry

Abstract

Quantum mechanical tunneling of atoms is increasingly found to play an important role in many chemical transformations. Experimentally, atom-tunneling can be indirectly detected by temperature-independent rate constants at low temperature or by enhanced kinetic isotope effects. On the contrary, using computational investigations the influence of tunneling on the reaction rates can directly be monitored. The tunnel effect, for example, changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition, and influences biochemical processes.

References in corpus (12)

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• Our astrochemical heritage
• Interstellar water chemistry: from laboratory to observations
• First detection of triply-deuterated methanol
• Kinetically Constrained Ring-Polymer Molecular Dynamics for Non-adiabatic Chemical Reactions
• Water Formation through a Quantum Tunneling Surface Reaction, OH + H2, at 10 K
• Quantum effects in the diffusion of hydrogen on Ru(0001)
• Quantum tunneling of oxygen atoms on very cold surfaces
• Efficient diffusive mechanisms of O atoms at very low temperatures on surfaces of astrophysical interest
• Diffusion Rates for Hydrogen on Pd(111) from Molecular Quantum Dynamics Calculations
• Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene
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Cited by in corpus (24)

• Quantum Simulators: Architectures and Opportunities
• Elucidating the NuclearQuantum Dynamics of Intramolecular Double Hydrogen Transfer in Porphycene
• Formation of the prebiotic molecule NH${}_2$CHO on astronomical amorphous solid water surfaces: accurate tunneling rate calculations
• Quantum tunneling during interstellar surface-catalyzed formation of water: the reaction H + H${}_2$O${}_2$ $\to$ H${}_2$O + OH
• Atom Tunneling in the Water Formation Reaction H${}_2$ + OH $\to$ H${}_2$O + H on an Ice Surface
• Reaction Rates and Kinetic Isotope Effects of H${}_2$ + OH $\to$ H${}_2$O + H
• Instanton Rate Constant Calculations Close to and Above the Crossover Temperature
• Dual-Level Approach to Instanton Theory
• Potential energy surface interpolation with neural networks for instanton rate calculations
• Rate constants from instanton theory via a microcanonical approach
• Quantum tunneling and level crossings in the squeeze-driven Kerr oscillator
• Comparison of classical reaction paths and tunneling paths studied with the semiclassical instanton theory
• Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions
• Calculation of Reaction Rate Constants in the Canonical and Microcanonical Ensemble
• Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications
• Tunnelling dominates the reactions of hydrogen atoms with unsaturated alcohols and aldehydes in the dense medium
• CRAHCN-O: A Consistent Reduced Atmospheric Hybrid Chemical Network Oxygen Extension for Hydrogen Cyanide and Formaldehyde Chemistry in CO2-, N2-, H2O-, CH4-, and H2-Dominated Atmospheres
• Quantum tunnelling in hydrogen atom transfer brings uncertainty to polymer degradation
• The role of atom tunneling in gas-phase reactions in planet-forming disks
• Variational principle for the determination of unstable periodic orbits and instanton trajectories at saddle points
• Reaching precise proton affinities in non-Born-Oppenheimer calculations
• Dissipative Berry phase effect in quantum tunneling
• Real-time dynamics with bead-Fourier path integrals I: Bead-Fourier CMD
• Isotopomer-Specific Carbon Isotope Ratio of Complex Organic Molecules in Star-Forming Cores