This journal is©The Royal Society of Chemistry 2016 Chem. Soc. Rev., 2016, 45, 3573--3575 | 3573

Cite this: Chem. Soc. Rev., 2016,

45, 3573

Surface reaction dynamics

Xueming Yanga and Alec M. Wodtkebc

The study of surface chemical reactiondynamics is crucial to many importantareas of research such as heterogeneouscatalysis, photocatalysis, material corro-sion and etching, to name just a few.Many fundamental questions, for exam-ple mechanisms of important catalyticreactions, rely on the study of surfacereaction dynamics. Prof. Gerhard Ertl’s

achievements in this area exemplify theimportance of this field. During the lastfew decades, the field of surface reactiondynamics has become one of the mostactive areas in fundamental physicalchemistry research. Surface reactiondynamics studies also have great potentialfor advancing our understanding of reac-tions on the surfaces of nanoparticles,which is badly needed. New frontiers havebeen developed during the past decades.New advanced surface experimental tech-niques have been developed to probesurface structures and chemical reactiondynamics at a much more detailed level.More detailed dynamics on very different

surfaces can be understood from thesenew experiments. On the other hand,theoretical efforts in surface chemicalreaction dynamics have also made sig-nificant advances, providing detailedmechanistic understanding of physicaland chemical processes at different inter-faces. It is quite hopeful that throughdetailed experimental and theoreticalstudies, studies of surface dynamics canreach a much higher level.

This themed issue includes ninereview papers on various topics in sur-face reaction dynamics; three of the ninepapers are tutorial reviews, written byleading experts in the field. In the first

a Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, 457 Zhongshan Rd., Dalian,

Liaoning, China 116023b Institut fur Physikalische Chemie, Tammannstrasse

6, 37077, Gottingen, Germanyc Dept. Dynamics at Surfaces, Max-Planck-Institut fur

biophysikalische chemie, Am Fassberg 11, 37077,

Gottingen, Germany

Xueming Yang

Xueming Yang obtained his PhDdegree (1986) at the University ofCalifornia, Santa Barbara. Afterpostdoctoral work at Princetonand Berkeley, he was appointedas an associate research fellowin 1995 and became a tenuredresearch fellow at the Institutefor Atomic and Molecular Sciencesin Taipei in 2000. In 2004, hemoved to the Dalian Instituteof Chemical Physics, ChineseAcademy of Sciences. He becamea fellow of American Physical

Society in 2006, and a member of the Chinese Academy ofScience in 2011. His speciality is developing advancedexperimental methods to investigate both gas-phase chemicaldynamics and surface reaction dynamics.

Alec M. Wodtke

Alec M. Wodtke received his BAdegree (1981) from the Universityof Utah in Chemistry. Heobtained his PhD degree (1986)in Physical Chemistry from UCBerkeley. From 1988–2010, hewas on the faculty of the Depart-ment of Chemistry & Biochemistryat the University of California,Santa Barbara. In 2010, he wasawarded the prestigious HumboldtProfessorship, which he assumedat the Georg-August University(Gottingen), also simultaneously

being appointed as a director at the Max Planck Institute forBiophysical Chemistry. He is known for his work in the field ofexperimental chemical dynamics, especially concerningvibrationally excited molecules on surfaces.

DOI: 10.1039/c6cs90049f

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3574 | Chem. Soc. Rev., 2016, 45, 3573--3575 This journal is©The Royal Society of Chemistry 2016

paper, Diesing and Hasselbrink (DOI:10.1039/c5cs00932d) have reviewed recentprogress in the study of surface metalheterostructures, such as metal–insulator–metal, metal–semiconductor and metal–semiconductor oxide–semiconductor het-erostructures, which have been used togain insights into the understanding ofenergy and charge transfer processes insurface chemistry on these surface struc-tures, particularly on the topic of surfacechemical reaction induced non-adiabaticprocesses that lead to the creation ofelectron-pairs and the dynamics of relatedenergy and charge redistribution.

In the second paper, Wodtke (DOI: 10.1039/c6cs00078a) has focused this reviewon the topic of electronically nonadiabaticinteractions between molecules and metalsurfaces. Such nonadiabatic interactionsare well known, particularly in the inter-action between diatomic molecules andmetal surfaces that molecular vibrationcan be strongly coupled to the electronsof the metal. However, how the couplingof nuclear motion to electrons can influ-ence chemical reaction probabilities isstill not well understood. This review hasprovided detailed accounts on this issueand discussed how the electronically non-adiabatic influence of chemical reactionscan be clearly demonstrated.

In the third paper by Morris andco-workers (DOI: 10.1039/c5cs00375j),recent advances in the heterogeneouschemistry of the most important atmo-spheric oxidants, O3, NO3, and OH, havebeen reviewed. These oxidants play acentral role in atmospheric chemistry,aerosols and the oxidation of materials.The paper provided a comprehensivereview on the recent experimental andcomputational studies on the detailedreaction mechanisms and kinetics forgas-phase oxidants’ interactions withorganic surfaces, using new researchmethods crossing the boundary betweensurface science and atmospheric chem-istry. It is encouraging to see that suchresearch will provide a more accurateand complete description of atmosphericchemistry.

In the chapter by Yang and coworkers(DOI: 10.1039/c5cs00448a), they haveprovided a comprehensive review on therecent studies of elementary reaction

processes of photocatalysis of importantmolecules such as water and methanolon single crystal TiO2 surfaces. Thereview is focused on studies of the rutileTiO2(110) surface, but some results ofother TiO2 surfaces are also provided.These studies have provided fundamen-tal insights into the elementary chemicalprocesses important to photocatalysis onTiO2, which will stimulate further inves-tigation into this important area. At theend of the review, a new dynamics-basedphotocatalysis model based on recentexperimental studies has also been dis-cussed, pointing out the need for moredefinitive surface chemistry studies inphotocatalysis.

In the fifth paper by Kroes and Dıaz(DOI: 10.1039/c5cs00336a), they havereviewed the state-of-the-art dynamicscalculations on the reactive scattering ofH2 from metal surfaces, which is animportant model system of elementaryreactions in heterogeneous catalysis, usingboth quantum and classical dynamicsmethods. These theoretical studies areperformed within the Born–Oppenheimerstatic surface model. Most calculationsare based on potential energy surfaces orforces computed with density functionaltheory (DFT) within the generalized gra-dient approximation to the exchange–correlation energy. The paper alsodescribes the accurate methods that havebecome available for molecule–surfaceinteraction in global PESs. It is nowpossible using these newly developedtools to study the dynamics of the H2 +metal surface reactions with chemicalaccuracy, providing deep insights intothe fundamental mechanism of thismodel surface chemical reaction.

In the paper by Guo and coworkers(DOI: 10.1039/c5cs00360a), they havefocused on the topic of dissociativechemisorption processes that are theinitial and rate-limiting step in manyheterogeneous processes. In this review,they have shown overwhelming experi-mental evidence that dissociative chemi-sorption is non-statistical in nature, andexcitations in different vibrational modeshave a huge effect on reactivity for chemi-sorption. Quantum dynamics methods cannow be used to investigate this process.The review provides an overview on recent

progress made in this area, especially inconstructing high-dimensional potentialenergy surfaces for polyatomic moleculeson transition metal surfaces and in quan-tum dynamical studies of dissociativechemisorption on these potential energysurfaces. Mode and bond selectivity indissociative chemisorption are empha-sized in the paper and are discussed usingthe recently proposed sudden vectorprojection model.

Faust and Nathanson (DOI: 10.1039/c6cs00079g), in their tutorial review, havedescribed experimental aspects of twotechniques for investigating the dynamicsof the interaction of gas phase moleculeswith liquid surfaces under vacuum condi-tions, liquid microjets and coated wheels.A historical survey of the two techniques isprovided in this review. In addition, thestrengths and shortcomings of each tech-nique are also discussed for scattering andevaporation experiments. Finally, recentmicrojet studies on the energy transferbetween O2 and liquid hydrocarbons, HCldissociation in salty water, and super-Maxwellian helium evaporation havebeen presented.

In the review by Hase and coworkers(DOI: 10.1039/c5cs00482a), two aspectsin the simulations of collisions of proto-nated peptide ions, peptide-H+, withorganic surfaces have been presented.The first aspect is a detailed descriptionof the classical trajectory chemicaldynamics simulation methodology, suchas MM, QM + MM, and QM/MM, to inves-tigate the peptide-H+ + surface collision.In another aspect, a few examples areprovided from the theoretical simulationson energy transfer, surface-induced disso-ciation, soft-landing, and reactive-landingfor peptide-H+ + surface collisions. Thesesimulations are in good agreement withexperiment, thus providing atomisticinterpretations of the peptide-H+ + surfacecollision dynamics.

In the final paper in this themed issue,Chadwick and Beck (DOI: 10.1039/c5cs00476d) present a tutorial review oftheir quantum state resolved experimentsdesigned to investigate gas–surface reac-tion dynamics. The experimental techni-ques used for state specific reactantpreparation and for the detection of sur-face bound reaction products developed

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in their laboratory are also described indetail. The review also provided excellentexamples of the studies of methane reac-tions on Ni and Pt surfaces, which showclear evidence of vibrational mode speci-ficity and bond selectivity, as well assteric effects in chemisorption reactions.These state-of-the-art experimental inves-tigations provide important benchmarksfor developing a detailed microscopicunderstanding of chemical reactivity atthe gas–surface interface.

From the nine reviews in this themedissue, which only represent a small part ofthe research carried out in the field, wecan see that surface reaction dynamicsstudies have gone far beyond the bound-ary of traditional surface chemistry, whichis more related to heterogeneous catalysis.

Not only can we now study gas phaseinteractions with metal surfaces at thequantum state specific level, studies onthe dynamics of molecular interactions onliquid surfaces, aerosols and organic sur-faces can also be carried out in great detailusing various techniques. This shows thatsurface reaction dynamics has a morebroad impact in the study of chemistryin different areas.

Another important trend in surfacereaction dynamics is the study of nona-diabatic surface dynamics in both thermaland photoinduced chemical reactions onsurfaces, and the experimental resultsshow that nonadiabatic surface processesare important in catalysis and photocata-lysis. We have also seen more powerfuland accurate theoretical tools have been

developed to understand surface chemicalreactions at the atomic and molecularlevel. These developments have pushedthe study of surface reaction dynamics toa new level. However, there are also greatchallenges in this field. Firstly, eventhough we have made significant progressin the study of surface reaction dynamicsunder well-controlled conditions, studiesof surface dynamics under more compli-cated conditions are still lacking. Sec-ondly, theoretical surface dynamicsrequire more accurate and powerful toolsto study surface processes with chemicalaccuracy (B1 kcal mol�1). We hope wecan directly meet these challenges in thestudy of surface reaction dynamicsthrough the development of new experi-mental and theoretical methods.

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