Excited state radiationless decay process with Duschinsky rotation effect: formalism and implementation.

Duschinsky rotation effect is a simple and effective way to characterize the difference between the ground state and excited state potential energy surfaces. For complex molecules, harmonic oscillator model is still the practical way to describe the dynamics of excited states. Based on the first-order perturbation theory a la Fermi golden rule, the authors have applied the path integral of Gaussian type for the correlation function to derive an analytic formalism to calculate the internal conversion rate process with Duschinsky rotation effect being taken into account. The validity of their formalism is verified through comparison with previous work, both analytically for the case of neglecting Duschinsky rotation and numerically for the ethylene molecules with two-mode mixing. Their expression is derived for multimode mixing.

[1]  N. Turro.  Modern Molecular Photochemistry , 1978 .

[2]  S. H. Lin,et al.  Effect of Partial Deuteration and Temperature on Triplet‐State Lifetimes , 1968 .

[3]  S. Peyerimhoff,et al.  Spin-forbidden transitions in the presence of an intersystem crossing: application to the b1Σ+ state in OH+ , 1987 .

[4]  Ian D. Williams,et al.  Hyperbranched Poly(phenylenesilolene)s:  Synthesis, Thermal Stability, Electronic Conjugation, Optical Power Limiting, and Cooling-Enhanced Light Emission , 2003 .

[5]  Haobin Wang,et al.  Multilayer formulation of the multiconfiguration time-dependent Hartree theory , 2003 .

[6]  S. Peyerimhoff,et al.  Theoretical study of radiative and predissociative processes in ArH and ArD , 1986 .

[7]  Daoben Zhu,et al.  Structures, electronic states, photoluminescence, and carrier transport properties of 1,1-disubstituted 2,3,4,5-tetraphenylsiloles. , 2005, Journal of the American Chemical Society.

[8]  A. Mebel,et al.  AB INITIO CALCULATIONS OF RADIATIONLESS TRANSITIONS BETWEEN EXCITED AND GROUND SINGLET ELECTRONIC STATES OF ETHYLENE , 1998 .

[9]  Yi Luo,et al.  Aggregation-enhanced luminescence and vibronic coupling of silole molecules from first principles , 2006 .

[10]  J. Yoshida,et al.  Triarylethene-based extended pi-systems: programmable synthesis and photophysical properties. , 2005, The Journal of organic chemistry.

[11]  Haiping Yu,et al.  The ground and first excited singlet state torsional potentials of 2-phenylindole from supersonic jet fluorescence spectra , 1997 .

[12]  A. Mebel,et al.  Ab Initio Calculations of Vibronic Spectra and Dynamics for Small Polyatomic Molecules: Role of Duschinsky Effect , 1999 .

[13]  Michael C. Zerner,et al.  An intermediate neglect of differential overlap technique for spectroscopy: Pyrrole and the azines , 1973 .

[14]  S. Fischer.  Anharmonicities in the theory of non-radiative transitions for polyatomic molecules , 1971 .

[15]  S. Lin,et al.  Radiationless transitions in isolated molecules , 1973 .

[16]  E. Pollak,et al.  Photoinduced Cooling of Polyatomic Molecules in an Electronically Excited State in the Presence of Dushinskii Rotations , 2004 .

[17]  S. Lin,et al.  Ultrafast Dynamics and Spectroscopy of Bacterial Photosynthetic Reaction Centers , 2002 .

[18]  W. Gelbart,et al.  Dependence of Radiationless Decay Rates in Polyatomic Molecules upon the Initially Selected Vibronic State: General Theory and Application , 1972 .

[19]  W. Siebrand.  Calculation of Franck–Condon Factors for Radiationless Transitions Based on Selective Excitation of Single Vibronic Levels , 1971 .

[20]  S. Lin,et al.  Study of vibronic, spin-orbit and vibronic-spin-orbit couplings of formaldehyde with applications to radiative and non-radiative processes , 1976, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[21]  C. DeWitt-Morette,et al.  Techniques and Applications of Path Integration , 1981 .

[22]  A. Nitzan,et al.  Optical Selection Studies of Radiationless Decay in an Isolated Large Molecule , 1971 .

[23]  B. Tang,et al.  Aggregation-Induced Emission of cis,cis-1,2,3,4-Tetraphenylbutadiene from Restricted Intramolecular Rotation , 2004 .

[24]  Joshua Jortner,et al.  The energy gap law for radiationless transitions in large molecules , 1970 .