By Ilya Prigogine, Stuart A. Rice
The Advances in Chemical Physics sequence offers the chemical physics box with a discussion board for severe, authoritative reviews of advances in each sector of the self-discipline. quantity 121 comprises the newest learn on polymer melts at strong surfaces, infrared lineshapes of susceptible hydrogen bonds, ab initio quantum molecular dynamics, and lots of different topics.
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Extra resources for Advances in Chemical Physics, Vol. 121
Similarly, we have rab ðtÞ ¼ Ca ðtÞCbÃ ðtÞ ¼ Ca ð0ÞCbÃ ð0ÞeÀ"hðEa ÀEb Þ eÀ2ðga þgb Þ ¼ rab ð0Þeitoba eÀgab t it t ð4:20Þ where gab is called the dephasing constant and is related to ga and gb as 1 1 1 1 þ gab ¼ ðga þ gb Þ ¼ ð4:21Þ 2 2 ta tb where ta and tb represent the lifetimes. In summary, we obtain d^ r i ^ ^r ^ À À^ ¼ À ½H 0; r dt h " ð4:22Þ 47 ultrafast dynamics and spectroscopy ^ is damping operator, and where À draa drbb ¼ Àga raa ; ¼ Àgb rbb dt dt drab 1 ¼ Àðioab þ gab Þrab ; gab ¼ ðga þ gb Þ 2 dt ð4:23Þ ð4:24Þ To show the importance of the damping operator, we apply the effective Hamiltonian to optical absorption.
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 ! e itof 0 ; i 2 Pi jhÂf 0 jÂi ij 0 D ! f ¼ jHfi0 j2 h " ð1 À1 dt fA ðtÞfD ðtÞ ð3:113Þ where for example, XX fA ðtÞ ¼ ! f 2p ¼ 2 jHfi0 j2 h " ð1 À1 ðAÞ dosif ðoÞ XX !
52, and the theoretical absorption spectra are calculated by using the electronic structures and interactions presented in the text and the vibrational properties adopted from the previous work. 22 s. h. lin et al. Figure 9 (Continued) electronic and vibrational properties listed in Tables I and III into Eq. Phe-a RC at various temperatures. Figure 9 compares the experimental absorption spectra at various temperatures with the corresponding calculated absorption spectra using the delocalized model with the thermal expansion model.
Advances in Chemical Physics, Vol. 121 by Ilya Prigogine, Stuart A. Rice