Pair-excitations

Our results also shed light on the long-lived PA3 band detected in transient PM measurements of P3BT (see Fig. 7-19) and can explain changes in the PA spectra observed in several ps transient measurements of films of PPV derivatives at energies around 1.8 eV [9, 25, 60J. In good PPV films the transient PA spectrum shows a PA band of excitons at 1.5 eV whose dynamics match those of the PL and stimulated emission (SE) [9J. However, in measurements of oxidized [25] or C60-doped films 60, there appears a new PA band at about 1.8 eV whose dynamics are not correlated with those of the PL and SE. Based on our A-PADMR results here, we attribute the new PA band at 1.8 eV to polaron pair excitations. These may be created via exciton dissociation at extrinsic defects such as carbo-... 

Using this model they have tried to look at important chemical processes at metal surfaces to deduce the role of electronic nonadiabaticity. In particular, they have tried to evaluate the importance of electron-hole-pair excitation in scattering, sticking and surface mobility of CO on a Cu(100) surface.36,37 Those studies indicated that the magnitude of energy transferred by coupling to the electron bath was significantly less than that coupled to phonons. Thus the role of electron-hole-pair excitation in... 

However, a very limited number of studies focused on the effect of solvent dynamics on electron transfer reactions at electrodes.Smith and Hynes" introduced the effect of electronic friction (arising from the interaction between the excited electron hole pairs in the metal electrode) and solvent friction (arising from the solvent dynamic [relaxation] effect) in the electron transfer rate at metallic electrodes. The consideration of electron-hole pair excitation in the metal without illumination by light seems unrealistic. 

In chemisorbed systems, the molecular orbitals of the adsorbate are mixed with the electronic states of the substrate, producing strong adsorption bonds, i.e. the frequency of the adsorbate mode is well above the highest phonon frequency of the substrate. The relaxation of these vibrational excited states via emission of substrate phonons has only a low probability, because many phonons have to be enoitted during the decay. Non-radiative damping by electron-hole pair excitation appears to be the dominant relaxation path in these systems. 

The strength of the lattice instability near the Fermi vector depends on the magnitude of the electron-phonon coupling and on the phase space available for electron-hole pair excitation around 2kf. Thus, a reconstructive surface phase transition has to fulfill the following requirements in order to be ascribed to an electronically driven lattice instability ... 

The resonance Raman enhancement profiles In Figures 7 and 8 show that the maximum Intensity of the Fe-O-Fe symmetric stretch falls to correspond to a distinct absorption maximum In the electronic spectrum. This Implies that the 0x0 Fe CT transitions responsible for resonance enhancement are obscured underneath other, more Intense bands. Although strong absorption bands In the 300-400 nm region (e > 6,000 M" cm"l) are a ubiquitous feature of Fe-O-Fe clusters, the Raman results make It unlikely that they are due to 0x0 -> Fe CT. An alternative possibility Is that they represent simultaneous pair excitations of LF transitions In both of the... 

X. Because there is damping of nuclear motion into e-h pairs, excited e-h pairs at electron temperature Te must also be able to excite nuclear coordinates by fluctuating forces Fx that satisfy the second fluctuation dissipation theorem given as... 

A special situation occurs at Zr (Z=40), where the neutron subshell closure (N=56) gives this nucleus a double subshell closure. Thus, particle-hole pair excitations across both subshell gaps are possible. This could produce situations much like those in doubly closed shell 0, in which the lowest-lying intruder deformed band has been shown to arise due to such excitations [BR064]. 

Hence the leading term in a single mode transition, i.e. the damping of the mode i of frequency Qi from the first excited level into the ground state by electron-hole pair excitation is given by the first term (see for example [36]) ... 

A method of calculating the correlation energy, intermediate between the IE PA approximation and the total pair excited variational function, has been described.157 The results of an application to XE+ BH are in good agreement with other calculations. 

In all dynamical simulations presented so far, it has been assumed that the electrons stay in their ground state throughout the whole process, i.e. the simulations have been based on the Born-Oppenheimer approximation. Still, at metal surfaces with their continuous spectrum of electronic states at the Fermi energy electron-hole (e-h) pair excitations with arbitrarily small energies are possible. However, the incorporation of electronically nonadiabatic effects in the dynamical simulation of the interaction dynamics of molecules with surface is rather difficult [2, 109, 110]. Hence the role of electron-hole pairs in the adsorption dynamics as an additional dissipation channel is still unclear [4],... 

Recent experiments determining the so-called chemicurrent [111] have provided some information on the importance of electron-hole pair excitation in adsorption processes. Using thin films deposited on n-type Si(l 1 1) as a Schottky diode device, the nonadiabatically generated electron-hole pairs upon both atomic and molecular chemisorption create the chemicurrent which can be measured [111, 112]. It has been estimated that for example in the NO adsorption on Ag one quarter of the adsorption energy is dissipated to electron-hole pairs. Adsorption-induced electron-hole pair creation has also been found for other metal substrates, such as Au, Pt, Pd, Cu, Ni and Fe, and even for semiconductors such as GaAs and Ge [112, 113]. 

Since DFT calculations are in principle only applicable for the electronic ground state, they cannot be used in order to describe electronic excitations. Still it is possible to treat electronic exciations from first principles by either using quantum chemistry methods [114] or time-dependent density-functional theory (TDDFT) [115,116], First attempts have been done in order to calculate the chemicurrent created by an atom incident on a metal surface based on time-dependent density functional theory [117, 118]. In this approach, three independent steps are preformed. First, a conventional Kohn-Sham DFT calculation is performed in order to evaluate the ground state potential energy surface. Then, the resulting Kohn-Sham states are used in the framework of time-dependent DFT in order to obtain a position dependent friction coefficient. Finally, this friction coefficient is used in a forced oscillator model in which the probability density of electron-hole pair excitations caused by the classical motion of the incident atom is estimated. 

Hopster H, Raue R, Kisker E et al (1983) Evidence for spin-dependent electron-hole-pair excitations in spin-polarized secondary-electron emission from Ni(l 10). Phys Rev Lett 50 70... 

As the region near an X-ray absorption edge is scanned in energy, the ejected photoelectron sequentially probes the empty electronic levels of the material. Theoretically, interest in core-state excitation has developed considerably since the work of Mahan (179) and Nozieres and De Dominicis (219) on the singular response of the conduction electrons (in metals) to the sudden potential created by removal of a core electron. The resulting electron-hole pair excitations lead to a threshold edge asymmetry. 

We are concerned with low-energy processes (near the Fermi energy). Consequently, the only pertinent wave vectors of electron-hole pair excitations will be those close to q = 0 and 2fcF since the electron-hole pair excitation energy is zero for these vectors in the one-dimensional noninteracting electron gas. The Fourier transform of the Coulomb interaction will contain terms near q = 0 and q = 2k which are approximated by... 

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