VIBRONIC EFFECTS IN ECD SPECTROSCOPY: FROM SINGLE CHROMOPHORES TO EXCITON DIMERS Fabrizio Santoro Italian National Research Council, ICCOM-CNR, Area della Ricerca del CNR di Pisa, fabrizio.santoro@iccom.cnr.it. One of our main research lines in recent years has been devoted to the development of efficient methods to compute the lineshape of electronic spectra of large systems (dozens of heavy atoms). Originally proposed for absorption [1], our methods have been extended and applied to chiral spectroscopies, like electronic circular dichroism (ECD) [2], magnetic circular dichroism (MCD) [3] and two-photon circular dichroism (TPCD) [4]. The implementation of a new time-dependent approach has allowed us to simulate the spectra of even larger systems, including temperature effects [5]. Our methodologies have been proven to be useful in a number of cases; we mention the investigation of the differences of the ECD of a series of cycloalkanones [6], the discrimination of electronic and vibronic bands in the ECD of alleno-acetylenic compounds [7], the proof that the characteristic alternation of signs of the ECD spectrum of the 1Lb benzene transition is determined by Herzberg-Teller effects and, finally, the analysis of the specificities of ECD spectra in systems whose chirality is engendered by isotopic substitution [8]. More recently, we worked out a different method tailored to simulate and interpret the vibronic shape of the ECD of exciton coupled dimers [9]. We are currently working to extend our methods to flexible systems and we believe that this can be of particular interest for chiral spectroscopies, potentially improving the description of the consequences due to conformational variety and large amplitude motions. In this contribution we will briefly present our expertise and discuss our next-future plans in this research field. 1. F. Santoro, R. Improta, A. Lami, J. Bloino, V.Barone, J. Chem. Phys. 126, 084509 (2007). 2. F. Santoro, V. Barone Int. J. Quantum. Chem 110, 624-636, (2010) 3. N. Lin, H. Solheim, X. Zhao, F. Santoro, K. Ruud J. Chem. Theor. Comp. 9, 1557-1567 (2013) 4. N. Lin, F. Santoro, A. Rizzo, Y. Luo, X. Zhao, , V. Barone J Phys. Chem A. 113, 4198-4207 (2009) 5. F. Avila, J. Cerezo, J. Soto, R. Improta, F. Santoro, Comp. Chem. Theor. 2014 6. P. Scafato, F. Caprioli, L. Pisani, D. Padula, F. Santoro, G. Mazzeo, S. Abbate, F. Lebon, G. Longhi, Tetrahedron 2013 10752-10762 7. P. Rivera-Fuentes, J.L. Alonso-Gómez, A. G. Petrovic, F. Santoro, N. Harada, N. Berova,F. F. Diederich, Angew. Chem. Int. Ed., 49, 2247-2250, (2010). 7. N. Lin, H. Solheim, K. Ruud, M. Nooijen, F. Santoro, X. Zhao, M. Kwit, P. Skowroneke Phys Chem Chem Phys 14, 3669-3680 (2012) 8. G. Pescitelli, V. Barone, L. Di Bari, A. Rizzo, F. Santoro J. Org. Chem. 78, 7398-7405, 2013 9. D. Padula, D. Picconi, A. Lami, G: Pescitelli, F. Santoro, J. Phys. Chem A 117 (2013) 3355-3368
Vibronic effects in ecd spectroscopy: from single chromophores to exciton dimers
Fabrizio Santoro
2014
Abstract
VIBRONIC EFFECTS IN ECD SPECTROSCOPY: FROM SINGLE CHROMOPHORES TO EXCITON DIMERS Fabrizio Santoro Italian National Research Council, ICCOM-CNR, Area della Ricerca del CNR di Pisa, fabrizio.santoro@iccom.cnr.it. One of our main research lines in recent years has been devoted to the development of efficient methods to compute the lineshape of electronic spectra of large systems (dozens of heavy atoms). Originally proposed for absorption [1], our methods have been extended and applied to chiral spectroscopies, like electronic circular dichroism (ECD) [2], magnetic circular dichroism (MCD) [3] and two-photon circular dichroism (TPCD) [4]. The implementation of a new time-dependent approach has allowed us to simulate the spectra of even larger systems, including temperature effects [5]. Our methodologies have been proven to be useful in a number of cases; we mention the investigation of the differences of the ECD of a series of cycloalkanones [6], the discrimination of electronic and vibronic bands in the ECD of alleno-acetylenic compounds [7], the proof that the characteristic alternation of signs of the ECD spectrum of the 1Lb benzene transition is determined by Herzberg-Teller effects and, finally, the analysis of the specificities of ECD spectra in systems whose chirality is engendered by isotopic substitution [8]. More recently, we worked out a different method tailored to simulate and interpret the vibronic shape of the ECD of exciton coupled dimers [9]. We are currently working to extend our methods to flexible systems and we believe that this can be of particular interest for chiral spectroscopies, potentially improving the description of the consequences due to conformational variety and large amplitude motions. In this contribution we will briefly present our expertise and discuss our next-future plans in this research field. 1. F. Santoro, R. Improta, A. Lami, J. Bloino, V.Barone, J. Chem. Phys. 126, 084509 (2007). 2. F. Santoro, V. Barone Int. J. Quantum. Chem 110, 624-636, (2010) 3. N. Lin, H. Solheim, X. Zhao, F. Santoro, K. Ruud J. Chem. Theor. Comp. 9, 1557-1567 (2013) 4. N. Lin, F. Santoro, A. Rizzo, Y. Luo, X. Zhao, , V. Barone J Phys. Chem A. 113, 4198-4207 (2009) 5. F. Avila, J. Cerezo, J. Soto, R. Improta, F. Santoro, Comp. Chem. Theor. 2014 6. P. Scafato, F. Caprioli, L. Pisani, D. Padula, F. Santoro, G. Mazzeo, S. Abbate, F. Lebon, G. Longhi, Tetrahedron 2013 10752-10762 7. P. Rivera-Fuentes, J.L. Alonso-Gómez, A. G. Petrovic, F. Santoro, N. Harada, N. Berova,F. F. Diederich, Angew. Chem. Int. Ed., 49, 2247-2250, (2010). 7. N. Lin, H. Solheim, K. Ruud, M. Nooijen, F. Santoro, X. Zhao, M. Kwit, P. Skowroneke Phys Chem Chem Phys 14, 3669-3680 (2012) 8. G. Pescitelli, V. Barone, L. Di Bari, A. Rizzo, F. Santoro J. Org. Chem. 78, 7398-7405, 2013 9. D. Padula, D. Picconi, A. Lami, G: Pescitelli, F. Santoro, J. Phys. Chem A 117 (2013) 3355-3368I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
