Hot electron-induced

While the importance of the breakdown of the BOA in thermal chemistry is still controversial, the time-reversed process of creating chemistry from hot electrons is well established. Because experiments are generally performed under conditions where there is no adiabatic chemistry, hot electron induced chemistry is easily identified and studied, even when the cross-section for the chemistry is very small. Typical scenarios involve photochemistry, femtochemistry and single molecule chemistry on surfaces. A few well-studied examples are discussed briefly in Section 4.8. Because a detailed discussion of these active fields would take this chapter far from its original purpose, they are only treated briefly to illustrate the relationship to other aspects of bond making/breaking at surfaces. 

Hot-electron-induced vibrational heating at surface - importance of a quantum-mechanical description. Surf. Sci., 341, L1031-L1036. 

Fig. 14.4. Schematic illustration of hot-electron effects (a) avalanche multiplication in the channel and (b) hot-electron-induced channel shortening...

ECL can also be generated via hot electrons emitted into electrolyte solution from an oxide-covered electrode surface, sometimes called a conductor/insulator/elec-trolyte surface [53]. This special light emission pathway in ECL is commonly known as hot-electron-induced ECL [54—56], where hot electrons are defined as... 

Silver nanoclusters exhibiting cathodic hot electron-induced ECL with considerable potential of its use as probes in molecular sensing have also been reported [109]. Most of the ECL studies have been performed using organic molecules however, few studies have been performed on organic NP ECL [110]. By direct reaction between HAuCLi and Imninol in aqueous solutions, luminol-reduced AuNPs have been synthesized, in recent years, where diameter of the NPs... 

Wu A-H, Sun J-J, Fang Y-M, Su X-L, Chen G-N (2010) Hot electron induced cathodic electrochemiluminescence at AuSb alloy electrode for fabricating immunosensor with self-assembled monolayers. Talanta 82(4) 1455-1461. doi 10.1016/j.talanta.2010.07.017... 

Spehar-Deleze AM, Suomi J, Jiang Q, De Rooij N, Koudelka-Hep M, Kulmala S (2006) Heterogeneous oligonucleotide-hybridization assay based on hot electron-induced electrochemiluminescence of a rhodamine label at oxide-coated aluminum and silicon electrodes. Electrochim Acta 51(25) 5438-5444. doi 10.1016/j.electacta.2006.02.017... 

HECL Hot electron-induced electrogenerated chemiluminescence HOMO Highest occupied molecular orbital LUMO Lowest unoccupied molecular orbital... 

The primary cathodic step of hot electron-induced electrochemiluminescence (HECL) was postulated to be an injection of hot electrons into aqueous electrolyte solution by tunnel emission through an insulating barrier, followed by reduction reactions induced either by presolvated hot electrons or by fully hydrated electrons [37, 38]. The introduction and details of this kind of hot electron electrochemistry and HECL has been reviewed very recently [33] and only short descriptions of the basic features are given here. 

Suomi J, Kulmala S (2009) Hot electron-induced electrochemiluminescence. Reviews in Fluorescence, in press (Chapter 3)... 

Kulmala S, Kulmala A, Helin M, Hyppanen I (1998) Hot electron-induced time-resolved electrogenerated luminescence of Tb(III) ions at stationary oxide-covered aluminium electrodes. Anal Chim Acta 359 71-86... 

Ala-Kleme T, Kulmala S, Vare L, Juhala P, Helin M (1999) Hot electron-induced electrogenerated chcaniluminesctaice of Ru(bpy)3 chelate at oxide-covered aluminum electrodes. Anal Chem 71 5538-5543... 

Helin M, Hakansson M, Canty P, Spehar A-M, Kulmala S (2002) Hot electron-induced electrogenerated chemiluminescence of l-amlnonaphtalene-4-sulphonate at oxide-covered aluminium electrodes in aqueous solution. Anal Chim Acta 454 193-201... 

Jiang Q, Spehar A-M, Hakansson M, Suomi J, Ala-Kleme T, Kulmala S (2006) Hot electron-induced cathodic chemiluminescence of rhodamine B at disposable oxide-coated aluminum electrodes. Electrochim Acta 51 2706-2714... 

Kulmala S, Ala-Kleme T, Latva M, Loikas K, Takalo H (1998) Hot electron-induced electrogenerated chemiluminescence of rare earth(III) chelates at oxide-covered aluminum electrodes. J Fluoresc 8 59-65... 

Eskola J, Makinen P, Oksa L, Loikas K, Nauma M, Jiang Q, Hakansson M, Suomi J, Kulmala S (2006) Competitive immunoassay by hot electron-induced electrochemiluminescence detection and using a semiautomatic electrochemiluminraneter. J Liunin 118 238-244... 

Peters T, Haeike C, Diesing D, Kovacs DA, Golczewski A, Kowarik G, Aumayr F, Wucher A, Schleberger M (2(X)8) Hot electrons induced by slow multiply cheuged ions. New J Phys 10 073019... 

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