Electron single-molecule

Stipe B C, Rezaei M A, Flo W, Gao S, Persson M and Lundqvist B I 1997 Single-molecule dissociation by tunneling electrons Rhys. Rev. Lett. 78 4410... 

Many of the most interesting current developments in electronic spectroscopy are addressed in special chapters of their own in this encyclopedia. The reader is referred especially to sections B2.1 on ultrafast spectroscopy. Cl.5 on single molecule spectroscopy, C3.2 on electron transfer, and C3.3 on energy transfer. Additional topics on electronic spectroscopy will also be found in many other chapters. 

Figure Cl.5.2. Fluorescence excitation spectra (cps = counts per second) of pentacene in /i-teriDhenyl at 1.5 K. (A) Broad scan of the inhomogeneously broadened electronic origin. The spikes are repeatable features each due to a different single molecule. The laser detuning is relative to the line centre at 592.321 nm. (B) Expansion of a 2 GHz region of this scan showing several single molecules. (C) Low-power scan of a single molecule at 592.407 nm showing the lifetime-limited width of 7.8 MHz and a Lorentzian fit. Reprinted with pennission from Moemer [198]. Copyright 1994 American Association for the Advancement of Science.

Chemical reactions can be studied at the single-molecule level by measuring the fluorescence lifetime of an excited state that can undergo reaction in competition with fluorescence. Reactions involving electron transfer (section C3.2) are among the most accessible via such teclmiques, and are particularly attractive candidates for study as a means of testing relationships between charge-transfer optical spectra and electron-transfer rates. If the physical parameters that detennine the reaction probability, such as overlap between the donor and acceptor orbitals. 

Figure C1.5.12.(A) Fluorescence decay of a single molecule of cresyl violet on an indium tin oxide (ITO) surface measured by time-correlated single photon counting. The solid line is tire fitted decay, a single exponential of 480 5 ps convolved witli tire instmment response function of 160 ps fwiim. The decay, which is considerably faster tlian tire natural fluorescence lifetime of cresyl violet, is due to electron transfer from tire excited cresyl violet (D ) to tire conduction band or energetically accessible surface electronic states of ITO. (B) Distribution of lifetimes for 40 different single molecules showing a broad distribution of electron transfer rates. Reprinted witli pennission from Lu andXie [1381. Copyright 1997 American Chemical Society.

Myers A B, Tchenio P and Moerner W E 1994 Vibronic spectroscopy of single molecules exploring electronic-vibrational frequency correlations within an inhomogeneous distribution J. Lumin. 58 161-7... 

Sauer M, Drexhage K H, Lieberwirth U, Muller R, Nerd S and Zander C 1998 Dynamics of the electron transfer reaction between an oxazine dye and DNA oligonucleotides motored on the single-molecule level Chem. Phys. Lett. 284 153-63... 

In the mid 1970s, Ugi and co-workers developed a scheme based on treating reactions by means of matrices - reaction (R-) matrices [16, 17]. The representation of chemical structures by bond and electron (BE-) matrices was presented in Section 2.4. BE-matrices can be constructed not only for single molecules but also for ensembles of them, such as the starting materials of a reaction, e.g., formaldehyde (methanal) and hydrocyanic add as shown with the B E-matrix, B, in Figure 3-12. Figure 3-12 also shows the BE-matrix, E, of the reaction product, the cyanohydrin of formaldehyde. 

Very recently, it has been reported that SWCNT can be synthesized by decomposition of benzene with Fe catalyst [27]. It would be of most importance to establish the controllability of the diameter and the helical pitch in this kind of synthesis of SWCNT toward the development of novel kinds of electronic devices such as single molecule transistor [41]. It can be said that this field is full of dream. 

To answer this question, it is necessary to consider the shape or spatial distribution of the orbitals filled by bonding electrons in molecules. From this point of view, we can distinguish between two types of bonding orbitals. Ihe first of these, and by far the more common, is called a sigma bonding orbital. It consists of a single lobe ... 

Lennard-Jones, J. E., J. Chem. Phys. 20, 1024, Spatial correlation of electrons in molecules. Study of spatial probability function using the single determinant. 

Similarly, we can write that for a combination of translational, rotational, vibrational, and electronic energy levels for a single molecule"... 

At its best, the study of solvent kies by the formalism given can be used to learn about proton content and activation in the transition state. For this reason it is known as the proton inventory technique. The kinetics of decay of the lowest-energy electronic excited state of 7-azaindole illustrates the technique.25 Laser flash photolysis techniques (Section 11.6) were used to evaluate the rate constant for this very fast reaction. From the results it was suggested that, in alcohol, a double-proton tautomerism was mediated by a single molecule of solvent such that only two protons are involved in the transition state. In water, on the other hand, the excited state tautomerism is frustrated such that two water molecules may play separate roles. Diagrams for possible transition states that can be suggested from the data are shown, where of course any of the H s might be D s. 

Representations showing electrons in molecules seem to suggest localisation of the valence electrons, but there are problematic issues in this regard. For example, we might ask if dioxygen has a double bond and two lone pairs on each O atom (as in Table 1.1) - a stmcture that does not reconcile with the paramagnetic nature of the substance - or a single bond and an odd number of electrons localised on each atom, as shown here ... 

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