Semiclassical study of electronically nonadiabatic dynamics in the condensed-phase: Spin-boson problem with Debye spectral density

1999 ◽  
Vol 110 (10) ◽  
pp. 4828-4840 ◽  
Author(s):  
Haobin Wang ◽  
Xueyu Song ◽  
David Chandler ◽  
William H. Miller
Keyword(s):  
Spectral Density ◽  
Condensed Phase ◽  
Nonadiabatic Dynamics

scholarly journals The Influence of Polarization on the Spectral Density

2019 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Spectral Density ◽  
Condensed Phase ◽  
Degrees Of Freedom ◽  
Nonlinear Optical ◽  
Energy Gap ◽  
Protein Complexes ◽  
Computational Cost ◽  
Spectral Densities ◽  
Excitation Energies ◽  
Vibrational Coupling

<p>Accurate spectral densities are necessary for computing realistic exciton dynamics and nonlinear optical spectra of chromophores in condensed phase environments, including multi-chromophore pigment-protein systems. However, due to the significant computational cost of computing spectral densities from first principles, requiring many thousands of excited state calculations, most simulations of realistic systems rely on treating the environment as fixed point charges. Here, using a number of representative systems ranging from solvated chromophores to the photoactive yellow protein (PYP), we demonstrate that the quantum mechanical (QM) polarization of the environment is key to obtaining accurate spectral densities and lineshapes within the cumulant framework. We show that the QM environment can enhance or depress the coupling of fast chromophore degrees of freedom to the energy gap, altering the electronic-vibrational coupling and the resulting vibronic progressions in the absorption spectrum. In analyzing the physical origin of peaks in the spectral density, we identify vibrational modes that couple the electron and the hole as being particularly sensitive to the QM screening of the environment. For PYP, we reveal the need for a careful determination of the appropriate QM region to obtain reliable spectral densities. Our results indicate that the QM polarization of the environment can be crucial not just for excitation energies, but also for electronic-vibrational coupling in complex systems, with implications for the correct modeling of linear and nonlinear optical spectroscopy in the condensed phase, as well as energy transfer in pigment-protein complexes.<br></p>

scholarly journals The Influence of Polarization on the Spectral Density

2019 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Spectral Density ◽  
Condensed Phase ◽  
Degrees Of Freedom ◽  
Nonlinear Optical ◽  
Energy Gap ◽  
Protein Complexes ◽  
Computational Cost ◽  
Spectral Densities ◽  
Excitation Energies ◽  
Vibrational Coupling

<p>Accurate spectral densities are necessary for computing realistic exciton dynamics and nonlinear optical spectra of chromophores in condensed phase environments, including multi-chromophore pigment-protein systems. However, due to the significant computational cost of computing spectral densities from first principles, requiring many thousands of excited state calculations, most simulations of realistic systems rely on treating the environment as fixed point charges. Here, using a number of representative systems ranging from solvated chromophores to the photoactive yellow protein (PYP), we demonstrate that the quantum mechanical (QM) polarization of the environment is key to obtaining accurate spectral densities and lineshapes within the cumulant framework. We show that the QM environment can enhance or depress the coupling of fast chromophore degrees of freedom to the energy gap, altering the electronic-vibrational coupling and the resulting vibronic progressions in the absorption spectrum. In analyzing the physical origin of peaks in the spectral density, we identify vibrational modes that couple the electron and the hole as being particularly sensitive to the QM screening of the environment. For PYP, we reveal the need for a careful determination of the appropriate QM region to obtain reliable spectral densities. Our results indicate that the QM polarization of the environment can be crucial not just for excitation energies, but also for electronic-vibrational coupling in complex systems, with implications for the correct modeling of linear and nonlinear optical spectroscopy in the condensed phase, as well as energy transfer in pigment-protein complexes.<br></p>

Nonadiabatic Dynamics of Condensed Phase Rate Processes

2006 ◽  
Vol 39 (1) ◽  
pp. 21-27 ◽  
Author(s):  
Gabriel Hanna ◽  
Raymond Kapral
Keyword(s):  
Condensed Phase ◽  
Nonadiabatic Dynamics ◽  
Rate Processes

Vibrational coherence and nonadiabatic dynamics in the condensed phase

2002 ◽  
Vol 116 (8) ◽  
pp. 3343-3352 ◽  
Author(s):  
C. R. Gonzalez ◽  
S. Fernandez-Alberti ◽  
J. Echave ◽  
M. Chergui
Keyword(s):  
Condensed Phase ◽  
Nonadiabatic Dynamics ◽  
Vibrational Coherence

Nonadiabatic Dynamics of Condensed Phase Rate Processes

ChemInform ◽  
2006 ◽  
Vol 37 (16) ◽  
Author(s):  
Gabriel Hanna ◽  
Raymond Kapral
Keyword(s):  
Condensed Phase ◽  
Nonadiabatic Dynamics ◽  
Rate Processes
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