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Advances in Chemical Physics, Vol. 121 - download pdf or read online

By Ilya Prigogine, Stuart A. Rice

The Advances in Chemical Physics sequence offers the chemical physics box with a discussion board for serious, authoritative reviews of advances in each zone of the self-discipline. quantity 121 comprises the newest learn on polymer melts at stable surfaces, infrared lineshapes of susceptible hydrogen bonds, ab initio quantum molecular dynamics, and plenty of different matters.

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Extra resources for Advances in Chemical Physics, Vol. 121

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P" h2 ÁEa ðn‘ 0Þ exp À kT l0 kT ð3:67Þ This equation is often used by Bixon and Jortner [77]. D. Applications to Photosynthetic RCs In 1991, Fleming and his co-workers have reported the temperature effect on the ET rate constants of Rb. capsulatus and its mutants (see Fig. 11 and Ref. 6). From Fig. 11, we can see that several species exhibit a pronounced inverse temperature Figure 11. Temperature effect on ET rates of Rb. capsulatas and its mutants. The data are reproduced from Ref. 6. 35 ultrafast dynamics and spectroscopy TABLE VI Vibrational Modes and Coupling Constants Transitions Vibrational Modes ——————————————————————————————— 100 224 750 1200 1400 1520 Coupling Constants P !

A special feature of the Marcus equation is that it predicts the parabolic dependence of the activation energy ÁEa on the free energy change ÁGfi ; that is, ÁEa is related to the free energy change ÁGfi in a parabolic form. The reason that ÁGfi ¼ Ef À Ei is due to the fact that our system consists of a collection of harmonic oscillators with displaced surfaces between the initial and final electronic states. In this case, the vibrational partition functions are the same between the initial and final electronic states.

F can be written as Iif ðoÞ ¼ 4ae o3 X X Pi jhÂf  0 j~ mfi jÂi ij2 dðof  0 ; i þ oÞ 3" hc3 Aif   0 ð3:109Þ where Aif denotes the radiative rate constant. f ¼ 9jAD j2 aa c4 Aif 8pe2 R6AD ae ð1 À1 do ðAÞ ðDÞ a ðoÞIif ðoÞ o4 if ð3:110Þ This is the famous Fo¨rster relation that expresses the singlet–singlet transition rate constant in terms of the spectral overlap of the emission spectra of D and absorption spectra of A. Next we consider the triplet–triplet transition. f 1 ¼ jHfi0 j2 h " ð1 dt À1 XX Â  XX  !

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