Vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation are computed in order to interpret and predict vibronic transitions that are probed in the Vibrationally Promoted Electronic Resonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem., Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformation of time-domain wavepacket autocorrelation functions, respectively. The time-independent approach uses a generalized version of the FCclasses method [F. Santoro et al., J. Chem. Phys. 126, 084509 (2007)]. In the time-dependent approach, autocorrelation functions are obtained by wavepacket propagation and by the evaluation of analytic expressions, within the harmonic approximation including Duschinsky rotation effects. For several medium-sized polyatomic systems, it is shown that selective pre-excitation of particular vibrational modes leads to a redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. This effect is typically most pronounced upon excitation of modes that are significantly displaced during the electronic transition, such as ring distortion modes within an aromatic π-system. Theoretical predictions as to which modes show the strongest VIPER effect are found to be in excellent agreement with experiment.
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Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy
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28 October 2017
Research Article|
October 30 2017
Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy
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JCP Editors' Choice 2017
Jan von Cosel;
Jan von Cosel
1
Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt
, Max-von-Laue-Str. 7, 60438 Frankfurt, Germany
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Javier Cerezo;
Javier Cerezo
2
Departamento de Química Física, Universidad de Murcia
, E-30071 Murcia, Spain
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Daniela Kern-Michler;
Daniela Kern-Michler
3
Institute of Biophysics, Goethe University Frankfurt
, Max-von-Laue-Str. 1, 60438 Frankfurt, Germany
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Carsten Neumann
;
Carsten Neumann
3
Institute of Biophysics, Goethe University Frankfurt
, Max-von-Laue-Str. 1, 60438 Frankfurt, Germany
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Luuk J. G. W. van Wilderen
;
Luuk J. G. W. van Wilderen
3
Institute of Biophysics, Goethe University Frankfurt
, Max-von-Laue-Str. 1, 60438 Frankfurt, Germany
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Jens Bredenbeck;
Jens Bredenbeck
3
Institute of Biophysics, Goethe University Frankfurt
, Max-von-Laue-Str. 1, 60438 Frankfurt, Germany
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Fabrizio Santoro;
Fabrizio Santoro
a)
4
Consiglio Nazionale delle Ricerche–CNR, Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), UOS di Pisa
, Via G. Moruzzi 1, I-56124 Pisa, Italy
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Irene Burghardt
Irene Burghardt
a)
1
Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt
, Max-von-Laue-Str. 7, 60438 Frankfurt, Germany
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a)
Authors to whom correspondence should be addressed: [email protected] and [email protected]
J. Chem. Phys. 147, 164116 (2017)
Article history
Received:
August 08 2017
Accepted:
October 11 2017
Citation
Jan von Cosel, Javier Cerezo, Daniela Kern-Michler, Carsten Neumann, Luuk J. G. W. van Wilderen, Jens Bredenbeck, Fabrizio Santoro, Irene Burghardt; Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy. J. Chem. Phys. 28 October 2017; 147 (16): 164116. https://doi.org/10.1063/1.4999455
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