Effective method to compute Franck-Condon integrals for optical spectra of large molecules in solution

2007 ◽  
Vol 126 (8) ◽  
pp. 084509 ◽  
Author(s):  
Fabrizio Santoro ◽  
Roberto Improta ◽  
Alessandro Lami ◽  
Julien Bloino ◽  
Vincenzo Barone
Keyword(s):  
Optical Spectra ◽  
Large Molecules ◽  
Franck Condon

scholarly journals Erratum: “Effective method to compute Franck-Condon integrals for optical spectra of large molecules in solution” [J. Chem. Phys. 126, 084509 (2007)]

2007 ◽  
Vol 126 (16) ◽  
pp. 169903 ◽  
Author(s):  
Fabrizio Santoro ◽  
Roberto Improta ◽  
Alessandro Lami ◽  
Julien Bloino ◽  
Vincenzo Barone
Keyword(s):  
Chem Phys ◽  
Optical Spectra ◽  
Large Molecules ◽  
Franck Condon

Effective method to compute vibrationally resolved optical spectra of large molecules at finite temperature in the gas phase and in solution

2007 ◽  
Vol 126 (18) ◽  
pp. 184102 ◽  
Author(s):  
Fabrizio Santoro ◽  
Alessandro Lami ◽  
Roberto Improta ◽  
Vincenzo Barone
Keyword(s):  
Gas Phase ◽  
Finite Temperature ◽  
Optical Spectra ◽  
Large Molecules

scholarly journals Optical Spectra in the Condensed Phase: Capturing Anharmonic and Vibronic Features Using Dynamic and Static Approaches

2019 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Andres Montoya-Castillo ◽  
Joseph Anthony Napoli ◽  
Thomas E. Markland ◽  
Christine Isborn
Keyword(s):  
Condensed Phase ◽  
Potential Energy Surfaces ◽  
Energy Gap ◽  
Time Correlation ◽  
Optical Spectra ◽  
Ab Initio Molecular Dynamics ◽  
Classical Dynamics ◽  
Dynamics Simulations ◽  
Energy Surfaces ◽  
Franck Condon

<p>Simulating optical spectra in the condensed phase remains a challenge for theory due to the need to capture spectral signatures arising from anharmonicity and dynamical effects, such as vibronic progressions and their induced asymmetry. As such, numerous simulation methods have been developed that invoke different approximations and vary in their ability to capture different physical regimes. Here we use several models of chromophores in the condensed phase and ab initio molecular dynamics simulations to rigorously assess the applicability of methods to simulate optical absorption spectra. Specifically, we focus on the ensemble scheme, which can address anharmonic potential energy surfaces but relies on the applicability of extreme nuclear-electronic timescale separation; the Franck-Condon method, which includes dynamical effects but only at the harmonic level; as well as the recently introduced ensemble zero-temperature Franck-Condon approach, which straddles these limits. We also devote particular attention to the performance of methods derived from a cumulant expansion of the energy gap fluctuations and test the ability to approximate the requisite time correlation functions using classical dynamics with quantum correction factors. These results provide insights as to when these methods are applicable and able to capture the features of condensed phase spectra qualitatively and, in some cases, quantitatively across a range of regimes.<br></p>

scholarly journals Optical Spectra in the Condensed Phase: Capturing Anharmonic and Vibronic Features Using Dynamic and Static Approaches

2019 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Andres Montoya-Castillo ◽  
Joseph Anthony Napoli ◽  
Thomas E. Markland ◽  
Christine Isborn
Keyword(s):  
Condensed Phase ◽  
Potential Energy Surfaces ◽  
Energy Gap ◽  
Time Correlation ◽  
Optical Spectra ◽  
Ab Initio Molecular Dynamics ◽  
Classical Dynamics ◽  
Dynamics Simulations ◽  
Energy Surfaces ◽  
Franck Condon

<p>Simulating optical spectra in the condensed phase remains a challenge for theory due to the need to capture spectral signatures arising from anharmonicity and dynamical effects, such as vibronic progressions and their induced asymmetry. As such, numerous simulation methods have been developed that invoke different approximations and vary in their ability to capture different physical regimes. Here we use several models of chromophores in the condensed phase and ab initio molecular dynamics simulations to rigorously assess the applicability of methods to simulate optical absorption spectra. Specifically, we focus on the ensemble scheme, which can address anharmonic potential energy surfaces but relies on the applicability of extreme nuclear-electronic timescale separation; the Franck-Condon method, which includes dynamical effects but only at the harmonic level; as well as the recently introduced ensemble zero-temperature Franck-Condon approach, which straddles these limits. We also devote particular attention to the performance of methods derived from a cumulant expansion of the energy gap fluctuations and test the ability to approximate the requisite time correlation functions using classical dynamics with quantum correction factors. These results provide insights as to when these methods are applicable and able to capture the features of condensed phase spectra qualitatively and, in some cases, quantitatively across a range of regimes.<br></p>

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