Reaction kinetics and dynamics articles within Nature Chemistry

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  • Article
    | Open Access

    Time-resolved femtosecond crystallography (TR-SFX) is a powerful technique to monitor structural transitions in protein crystals at the atomic level, but its use in non-protein synthetic materials remains limited. Now TR-SFX has been used to visualize the structural dynamics of metal–organic frameworks, showing the potential of this tool to study the dynamic motion of crystalline porous materials.

    • Jaedong Kang
    • , Yunbeom Lee
    •  & Hyotcherl Ihee

  • Article |

    Although photoinduced concerted multiple-bond-rotation processes are known in photoactive biological systems, the synthesis of compounds exhibiting similar behaviour has proven challenging. Now a thioamide-based system featuring chalcogen substituents has been shown to exhibit photoinduced C–N/C–C rotation; the rotation mode can be switched depending on external stimuli such as temperature and light irradiation.

    • Shotaro Nagami
    • , Rintaro Kaguchi
    •  & Akira Katsuyama

  • Article |

    Although interfacial proton-coupled electron transfers are critical reaction steps in chemical and biological processes, studies investigating these reactions are complicated by surface heterogeneity. Now, interfacial proton-coupled electron transfer kinetics are studied and modelled at isolated, well-defined active sites to provide a foundation for understanding complex reactions involved in energy conversion and catalysis.

    • Noah B. Lewis
    • , Ryan P. Bisbey
    •  & Yogesh Surendranath

  • Research Briefing |

    Trans–cis photoisomerization is a fundamental photochemical reaction that is thought to proceed through an intermediate with a perpendicular conformation. However, unambiguous identification of this state has proved challenging. The combination of state-of-the-art ultrafast spectroscopy and quantum chemical calculations now provides evidence for its structural observation in stilbene photoisomerization.

  • Article |

    The prototypical trans–cis photoisomerization of stilbenes is thought to occur via a transient intermediate with a perpendicular conformation—often called ‘the phantom state’—but its unambiguous identification has thus far proved difficult. Now, using ultrafast ultraviolet Raman spectroscopy and ab initio molecular dynamics simulation, evidence for its existence and its perpendicular conformation has been obtained.

    • Hikaru Kuramochi
    • , Takuro Tsutsumi
    •  & Tahei Tahara

  • Article |

    Many natural products are produced by non-ribosomal peptide synthetases in an assembly-line fashion. How these molecular machines orchestrate the biochemical sequences has remained elusive. It is now understood that an extended-conformation ensemble is needed to coordinate chemical-transformation steps whereas the biosynthesis directionality is driven by the enzyme’s innate conformational free energies.

    • Xun Sun
    • , Jonas Alfermann
    •  & Haw Yang

  • News & Views |

    When atoms first appeared in the Universe, molecules were needed to help coalesce them into stars. The trihydrogen cation H3+ is among the prime candidates for that process, and now two independent studies provide detailed insight into the ultrafast dynamics of the formation of this important ion from two hydrogen molecules.

    • Marcos Dantus

  • News & Views |

    Although Li–O2 batteries offer high theoretical energy storage capacities, few approach these limits. Now, a class of redox mediators is shown to send the discharge reaction from the electrode surface into the electrolyte solution, boosting device capacities and providing selection criteria for future efforts.

    • Zhangquan Peng

  • Article |

    Wavepacket dynamics around conical intersections are influenced by geometric phase, which can affect chemical reaction outcomes but has only been observed through indirect signatures. Now, by engineering a controllable conical intersection in a trapped-ion quantum simulator, the destructive wavepacket interference caused by a geometric phase has been observed.

    • C. H. Valahu
    • , V. C. Olaya-Agudelo
    •  & I. Kassal

  • News & Views |

    Scientists have been studying how polymers break in solutions for decades, but the mechanism by which chains are stretched to the point of covalent bond scission is not trivial. Now, an experiment series provides ample support for a dynamic model in which chains uncoil from end to middle, while concurrently relaxing.

    • Charles E. Diesendruck

  • Article |

    Although gas bubble dynamics during electrochemical processes dramatically affect performance, the fundamental understanding and manipulation of such dynamics have been limited. Now, electrolyte composition is found to be a key factor in inducing a solutal Marangoni instability that impacts both H2 gas detachment and coalescence between H2 microbubbles.

    • Sunghak Park
    • , Luhao Liu
    •  & Marc T. M. Koper

  • Article
    | Open Access

    Pump–probe measurements conventionally achieve femtosecond time resolution for X-ray crystallography of reactive processes, but the measured structural dynamics are complex. Using coherent control techniques, we show that the ultrafast crystallographic differences of a fluorescent protein are dominated by ground-state vibrational processes that are unconnected to the photoisomerization reaction of the chromophore.

    • Christopher D. M. Hutchison
    • , James M. Baxter
    •  & Jasper J. van Thor

  • Research Briefing |

    Despite advances, understanding of the quantum state-to-state scattering dynamics between charged ions and neutral molecules at low collision energies remains limited. A high-resolution crossed-beam experiment with quantum state-selected ions prepared by laser photoionization and supporting trajectory surface-hopping calculations now provides insight into the quantum state-to-state collisional dynamics of a model charge-transfer reaction.

  • Article |

    Quantum state-to-state understanding of collisional charge transfer is a long-time goal of chemical dynamics. Now, using high-resolution molecular-beam experiments with spin–orbit state-selected ions and surface-hopping calculations, a vibrational-state-specific mechanism has been observed for the reaction Ar+(2P3/2) + N2 → Ar + N2+(v′, J′). Besides the well-known long-range harpooning mechanism, a hard-collision glory scattering mechanism was also identified.

    • Guodong Zhang
    • , Dandan Lu
    •  & Hong Gao

  • Article |

    Rapid solvent flows stretch dissolved polymer chains to their breaking point by hitherto-elusive molecular mechanisms. Now, analysis of competing mechanochemical reactions suggests a broad distribution of molecular geometries of fracturing chains. This occurs because, in each chain, fracture and kinetically destabilizing backbone stretching compete on submillisecond timescales.

    • Robert T. O’Neill
    •  & Roman Boulatov

  • Article |

    Trihydrogen cations are abundant in interstellar space and play a vital role in both star and organic molecule formation. Now it has been shown that D3+ cations can be directly produced through photoionization of molecular D2–D2 dimers.

    • Yonghao Mi
    • , Enliang Wang
    •  & André Staudte

  • Article |

    H3+ and D3+ serve as initiators of many chemical reactions in interstellar clouds. Now the ultrafast formation dynamics of D3+ from a light-driven bimolecular reaction starting from D2–D2 dimers have been measured. It has also been shown that the emission direction of D3+ can be controlled by driving the reaction with a more complex two-colour laser pulse.

    • Lianrong Zhou
    • , Hongcheng Ni
    •  & Jian Wu

  • Article |

    The transition state, a transient species where bond transformation occurs, fundamentally controls reaction dynamics. This important species can be probed through the photodetachment of an anionic precursor, as has now been shown in the F + NH3 reaction. A combination of theory and experiment reveals resonances that span the transition state.

    • Mark C. Babin
    • , Martin DeWitt
    •  & Daniel M. Neumark

  • Article
    | Open Access

    Inelastic hydrogen atom scattering from surfaces provides a good benchmark for the validity of the Born–Oppenheimer approximation in surface chemistry. Now it has been shown that hydrogen atoms colliding with a semiconductor surface can efficiently excite electrons above the surface bandgap, representing a clear example of the failure of the approximation.

    • Kerstin Krüger
    • , Yingqi Wang
    •  & Oliver Bünermann

  • Article |

    Intersystem crossing in reaction entrance channels usually arises from ‘heavy-atom’ effects. Now molecular-beam experiments show that even without heavy atoms, the O(3P) + pyridine reaction leads to spin-forbidden pyrrole + CO products. Theoretical calculations reveal efficient intersystem crossing before the entrance barrier for O-atom addition to the N-atom lone pair, which dominates reactivity at low to moderate temperatures.

    • Pedro Recio
    • , Silvia Alessandrini
    •  & Vincenzo Barone

  • Article |

    The influence that liquid environments have on the ultrafast excited-state dynamics of molecules is poorly understood. Using time-resolved photoelectron spectroscopy, the dynamics of the photoisomerization of stilbene in the gas and liquid phases have now been shown to be qualitatively similar—including the observation of vibrational coherences—but the timescales are significantly longer in the liquid phase.

    • Chuncheng Wang
    • , Max D. J. Waters
    •  & Hans Jakob Wörner

  • Article |

    HCN and its isomer HNC are both observed in the interstellar medium and inelastic collisions with helium and other species strongly influence their derived abundances. Now it has been shown experimentally and theoretically that HNC is much more strongly excited than HCN in collisions with helium at the low temperatures of interstellar space.

    • Brian M. Hays
    • , Divita Gupta
    •  & Ian R. Sims

  • Article |

    The collision dynamics between a pair of aligned molecules in the presence of a scattering resonance provide the most sensitive probe of the long-range anisotropic forces important to chemistry. By simultaneously controlling the collision temperature and geometry between a pair of aligned D2 molecules, we unravel the anisotropic dynamics of a cold scattering process.

    • Haowen Zhou
    • , William E. Perreault
    •  & Richard N. Zare

  • Article |

    Influencing the products of a reaction through controlling the state of the reactants is a notable goal for chemists. It has now been shown that the reactivity of a pair of Fermi-coupled vibrational states of CH3D(v1-I and v1-II) with a chlorine atom depends not only on the constituent basis modes, but also on the relative phase of the two modes in their wave-functions.

    • Huilin Pan
    •  & Kopin Liu

  • Article |

    Low-energy NO–He collisions have been studied and scattering resonances observed. By rotationally exciting NO before the collision, a controlled amount of angular momentum was added and its release in de-excitation collisions was monitored—additional quantum waves were imprinted in the angular distributions of the scattering products.

    • Tim de Jongh
    • , Quan Shuai
    •  & Sebastiaan Y. T. van de Meerakker

  • Article |

    Aromatic systems that interact non-covalently are important in many settings, such as base-pair stacking and DNA–drug interactions; however, their excited-state molecular dynamics are not fully understood. Now, intermolecular Coulombic decay in benzene dimers has been observed. The process is initiated by electron-impact ionization and proceeds through ultrafast energy transfer between the benzene molecules.

    • Xueguang Ren
    • , Jiaqi Zhou
    •  & Alexander Dorn

  • News & Views |

    Atmospheric chemists have been unable to explain the rapid sulfate formation observed during wintertime aerosol pollution events. Now, kinetic measurements in atmospherically relevant aerosol particles have highlighted a significant role for nitrogen dioxide in sulfate formation via its interfacial reaction with dissolved SO2.

    • Jian Zhen Yu

  • Article |

    As the number of atoms involved in a reaction increases, so do the experimental and theoretical challenges faced when studying their dynamics. Now, using ion-imaging experiments and quasi-classical trajectory simulations, the dynamics of the polyatomic reaction F– + CH3CH2Cl have been studied and the competition between bimolecular nucleophilic substitution and base-induced elimination has been disentangled.

    • Jennifer Meyer
    • , Viktor Tajti
    •  & Roland Wester

  • Article
    | Open Access

    The breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry and detailed understanding of non-adiabatic dynamics is still incomplete. Now, the non-adiabatic quenching of electronically excited OH(A2Σ+) molecules by H2 has been investigated using full-dimensional quantum dynamics calculations and a high-quality diabatic-potential-energy matrix, providing insight into the branching ratio of the two electronic quenching channels.

    • Bin Zhao
    • , Shanyu Han
    •  & Hua Guo

  • News & Views |

    Controlling reactions between molecules is a major fundamental goal in chemistry and doing so on the level of individual quantum states is very challenging. Now, control over the reactant state and full characterization of the product-state distribution of an ultracold bimolecular reaction has been demonstrated.

    • Andreas Osterwalder

  • News & Views |

    The physical properties of a liquid at an interface differ from bulk solution limits, but how this affects chemical reactivity is unclear. Now, ultrafast, surface-sensitive vibrational spectroscopy has revealed that the light-induced reaction of phenol with water is four orders of magnitude faster at the water surface than in bulk.

    • Robert A. Walker

  • Article |

    Reactions at the interface between water and other phases play important roles in various chemical settings. Now, ultrafast phase-sensitive interface-selective vibrational spectroscopy has revealed that the photoionization of phenol can occur four orders of magnitude faster at the water surface than in the bulk aqueous phase.

    • Ryoji Kusaka
    • , Satoshi Nihonyanagi
    •  & Tahei Tahara

  • Article |

    Energy scrambling in intermediate complexes—which form in many chemical reactions—presents a major challenge to state-to-state control. However, nuclear spin tends to remain unchanged throughout reactions and now, by manipulating the reactants’ nuclear spins using an external magnetic field, control over the product state distribution of a bimolecular reaction has been demonstrated.

    • Ming-Guang Hu
    • , Yu Liu
    •  & Kang-Kuen Ni

  • Article |

    Metallocenes are attractive mechanophores because they are stable in the absence of force, yet reactive under tension. Now, covalently bridging the two cyclopentadienyl (Cp) ligands of ferrocenes embedded in a polymer has been shown to alter their mechanochemical reactivity, leading to a faster dissociation of the Fe–Cp bond, which occurs through a peeling mechanism rather than a shearing one.

    • Yudi Zhang
    • , Zi Wang
    •  & Stephen L. Craig

  • Article |

    Low-temperature scattering leads to the formation of quantum resonances or quasi-bound states, which are observable as peaks in the measured collision cross-sections. Now it has been shown that two different formation mechanisms, quantum tunnelling and quantum reflection, can be distinguished by measuring and comparing elastic and inelastic scattering, which probe the spatial localization of the resonance wavefunctions.

    • Prerna Paliwal
    • , Nabanita Deb
    •  & Edvardas Narevicius

  • News & Views |

    How atoms organize during the earliest stages of nucleation has been a subject of speculation for over a century. Using atomically resolved electron microscopy, the formation and ordering of metal clusters from individual atoms has now been observed in carbon nanotubes that serve as ‘test tubes’.

    • J. J. De Yoreo
    •  & B. A. Legg

  • Article |

    Crystal symmetry is notoriously uncorrelated to the symmetry of the constituent molecules that make up a crystal. Symmetry breaking is typically thought to occur during nucleation and growth, but a symmetry element of olanzapine crystals—an inversion centre—has now been shown to emerge in centrosymmetric dimers extant in solution prior to crystallization.

    • Monika Warzecha
    • , Lakshmanji Verma
    •  & Peter G. Vekilov

  • Article |

    Crystal nucleation processes are difficult to probe experimentally because of the spatial and temporal scales involved. Now, the heterogeneous nucleation of three different metals has been observed by electron microscopy with atomic resolution—using single-walled carbon nanotube as test tubes—and, in each case, shown to adopt a two-step nucleation mechanism involving a metastable amorphous precursor.

    • Kecheng Cao
    • , Johannes Biskupek
    •  & Ute Kaiser

  • Article |

    Controlling single-molecule magnets (SMMs) with ultrashort laser pulses could be key to future data storage devices, however, the photophysics of SMMs is complex. Now, using a monomer model system, it has been shown that optical excitation of Mn(iii)-SMMs leads to a modulation of the Jahn–Teller distortion, which is important for its magnetic anisotropy.

    • Florian Liedy
    • , Julien Eng
    •  & J. Olof Johansson

  • Article |

    Understanding how structural dynamics contribute to protein function is a longstanding challenge in structural biology. Now, time-resolved X-ray solution scattering following an infrared laser-induced temperature jump has been used to probe functional, intramolecular motions in the dynamic enzyme cyclophilin A.

    • Michael C. Thompson
    • , Benjamin A. Barad
    •  & James S. Fraser

  • News & Views |

    Precipitation processes enable the fast preparation of a variety of inorganic materials, although typically with little control over their morphology. Now, their one-, two- or three-dimensional growth has been promoted simply by tuning the electrolytic dissociation of the reactants and the supersaturation of the solution.

    • Mihui Park
    • , Gi-Hyeok Lee
    •  & Yong-Mook Kang

  • Article |

    Precipitation enables the straightforward production of a variety of inorganic materials, but the rapid reaction rates involved typically make controlling their morphologies difficult. Now, the growth of either one-, two- or three-dimensional materials has been promoted by tuning of the reactants’ electrolytic dissociation and solution supersaturation, without the need for capping agents and templates.

    • Wei-Hong Lai
    • , Yun-Xiao Wang
    •  & Shi-Xue Dou

  • Article |

    Quantum coherence and dephasing in molecular motions determine the behaviour of many chemical reactions and are the fundamental basis for the concept of coherent control. Now, ultrafast X-ray scattering combined with a detailed structural determination analysis precisely measures the coherent vibrational motions of a polyatomic organic molecule following photoexcitation.

    • Brian Stankus
    • , Haiwang Yong
    •  & Peter M. Weber

  • Article |

    The F + para-H2 → HF + H reaction is an important source of HF in interstellar clouds; however, its unusually high rate and its dynamics at low temperature are not fully understood. Now, quantum-state resolved crossed-beam scattering measurements and anion photoelectron spectroscopy have revealed that this reactivity is caused by a resonance-enhanced tunnelling effect involving a post-barrier resonance state.

    • Tiangang Yang
    • , Long Huang
    •  & Daniel M. Neumark

  • News & Views |

    Light is often used to trigger reactions, energetically exciting the reactant(s) to kick them over the intrinsic reaction barrier. Now, however, the reaction between an excited atom and a charged molecule at very low temperatures has been shown not to adhere to this paradigm, instead undergoing a reaction blockading effect.

    • Roland Wester

  • Article |

    The relative orientation of molecules when they collide is of particular interest to chemists as it provides information on the preferred collision mechanism. Now, experiments in which NO molecules are oriented sideways to incoming Ar atoms show that the spatial manipulation of the collision partners provides a means to control the scattering outcome.

    • Cornelia G. Heid
    • , Victoria Walpole
    •  & F. Javier Aoiz

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