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 quarter of the self-discipline. quantity 121 includes the most recent examine on polymer melts at sturdy surfaces, infrared lineshapes of susceptible hydrogen bonds, ab initio quantum molecular dynamics, and lots of different topics.
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Extra info for Advances in Chemical Physics, Vol. 121
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. In this case, we have ^ ¼H ^ 0 þ VðtÞ ^ H ð4:25Þ ^ denotes the interaction between the system and radiation ﬁeld: where VðtÞ ^ ¼ À~ VðtÞ mÁ~ EðtÞ ð4:26Þ Here ~ m is dipole operator and ~ EðtÞ is electric ﬁeld in optical radiation.
1, Eq. m ¼ 2 ð3:21Þ dðomk Þ H þ hokn " h m mk " m n B. Electron and Energy Transfers In the study of the ultrafast dynamics of photosynthetic bacterial reaction centers, we are concerned with the photoinduced electron transfer  "ho DA À! DÃ A ! Dþ AÀ ð3:22Þ and energy transfer "ho DA À! DÃ A ! DAÃ ð3:23Þ ultrafast dynamics and spectroscopy 27 Figure 10. Vibronic levels of an electron transfer system. Here the initial electronic state is the DÃ A state and the ﬁnal electronic state is the Dþ AÀ charge separation state.
F ¼ X X Y 2p o‘ 0 0 0 0 jR‘ ðfiÞj2 Pi jhwf 0j jwij ij2 h 2"h " j 0 0 0 Â ½" ‘ dðÀ" ho‘ þ Ef0 0 À Ei Þ þ ð" ‘ þ 1Þdð"ho‘ þ Ef0 0 À Ei Þ ð3:76Þ For the displaced oscillator model, Eq. f ¼ ð1 1 o‘ 2 jR ð fiÞj dteitofi ½" ‘ eÀito‘ þ ð" ‘ þ 1Þeito‘ ‘ h h2 2" " À1 " # X Àitoj itoj 0 Â exp À Sj fð2" nj þ 1Þ À " nj e À ð"nj þ 1Þe g ð3:77Þ j It should be noted that usually " ho‘ =kT ) 1; at this limit, Eq. 76) or Eq. 77) reduces to X X Y 2p o‘ 2 0 0 0 0 0 jR ð fiÞj Pi jhwf 0j jwij ij2 dð"ho‘ þ Ef0 0 À Ei Þ ‘ 2 2" h h " 0 j ð1 1 o‘ ¼ 2 jR‘ ð fiÞj2 dt exp itðofi þ o‘ Þ h h 2" " À1 !
Advances in Chemical Physics, Vol. 121 by Ilya Prigogine, Stuart A. Rice