Top Curr Chem (Z) (2018) 376:24
https://doi.org/10.1007/s41061-018-0201-8
1 3
REVIEW
Towards Accurate Simulation of Two‑Dimensional
Electronic Spectroscopy
Javier Segarra‑Martí
1
· Shaul Mukamel
2
· Marco Garavelli
3
· Artur Nenov
3
·
Ivan Rivalta
1
Received: 21 December 2017 / Accepted: 24 April 2018 / Published online: 1 June 2018
© Springer International Publishing AG, part of Springer Nature 2018
Abstract We introduce the basic concepts of two-dimensional electronic spectroscopy (2DES) and a general theoretical framework adopted to calculate, from first principles, the nonlinear response of multi-chromophoric systems in realistic environments.
Specifically, we focus on UV-active chromophores representing the building blocks of
biological systems, from proteins to nucleic acids, describing our progress in developing computational tools and protocols for accurate simulation of their 2DUV spectra.
The roadmap for accurate 2DUV spectroscopy simulations is illustrated starting with
benchmarking of the excited-state manifold of the chromophoric units in a vacuum,
which can be used for building exciton Hamiltonians for large-scale applications or as
a reference for first-principles simulations with reduced computational cost, enabling
treatment of minimal (still realistic) multi-chromophoric model systems. By adopting
a static approximation that neglects dynamic processes such as spectral diffusion and
population transfer, we show how 2DUV is able to characterize the ground-state conformational space of dinucleosides and small peptides comprising dimeric chromophoric
units (in their native environment) by tracking inter-chromophoric electronic couplings.
Recovering the excited-state coherent vibrational dynamics and population transfers,
* Marco Garavelli
* Artur Nenov
* Ivan Rivalta
ivan.rivalta@ens-lyon.fr
1
Université de Lyon, École Normale Supérieure de Lyon, CNRS, Université Claude Bernard
Lyon 1, Laboratoire de Chimie UMR 5182, 69342 Lyon, France
2
Department of Chemistry, University of California, Irvine, CA 92697-2025, USA
3
Dipartimento di Chimica Industriale, Università degli Studi di Bologna, Viale del Risorgimento
4, 40136 Bologna, Italy
63
Reprinted from the journal
Chapter 3 was originally published as Segarra-Martí, J., Mukamel, S., Garavelli, M., Nenov, A. & Rivalta, I.
Top Curr Chem (Z) (2018) 376: 24. https://doi.org/10.1007/s41061-018-0201-8.
https://doi.org/10.1007/s41061-018-0201-8
1 3
REVIEW
Towards Accurate Simulation of Two‑Dimensional
Electronic Spectroscopy
Javier Segarra‑Martí
1
· Shaul Mukamel
2
· Marco Garavelli
3
· Artur Nenov
3
·
Ivan Rivalta
1
Received: 21 December 2017 / Accepted: 24 April 2018 / Published online: 1 June 2018
© Springer International Publishing AG, part of Springer Nature 2018
Abstract We introduce the basic concepts of two-dimensional electronic spectroscopy (2DES) and a general theoretical framework adopted to calculate, from first principles, the nonlinear response of multi-chromophoric systems in realistic environments.
Specifically, we focus on UV-active chromophores representing the building blocks of
biological systems, from proteins to nucleic acids, describing our progress in developing computational tools and protocols for accurate simulation of their 2DUV spectra.
The roadmap for accurate 2DUV spectroscopy simulations is illustrated starting with
benchmarking of the excited-state manifold of the chromophoric units in a vacuum,
which can be used for building exciton Hamiltonians for large-scale applications or as
a reference for first-principles simulations with reduced computational cost, enabling
treatment of minimal (still realistic) multi-chromophoric model systems. By adopting
a static approximation that neglects dynamic processes such as spectral diffusion and
population transfer, we show how 2DUV is able to characterize the ground-state conformational space of dinucleosides and small peptides comprising dimeric chromophoric
units (in their native environment) by tracking inter-chromophoric electronic couplings.
Recovering the excited-state coherent vibrational dynamics and population transfers,
* Marco Garavelli
* Artur Nenov
* Ivan Rivalta
ivan.rivalta@ens-lyon.fr
1
Université de Lyon, École Normale Supérieure de Lyon, CNRS, Université Claude Bernard
Lyon 1, Laboratoire de Chimie UMR 5182, 69342 Lyon, France
2
Department of Chemistry, University of California, Irvine, CA 92697-2025, USA
3
Dipartimento di Chimica Industriale, Università degli Studi di Bologna, Viale del Risorgimento
4, 40136 Bologna, Italy
63
Reprinted from the journal
Chapter 3 was originally published as Segarra-Martí, J., Mukamel, S., Garavelli, M., Nenov, A. & Rivalta, I.
Top Curr Chem (Z) (2018) 376: 24. https://doi.org/10.1007/s41061-018-0201-8.