Toward assessment of density functionals for vibronic coupling in two-photon absorption: A case study of 4-nitroaniline

Robert Zaleśny, Guangjun Tian, Christof Hättig, Wojciech Bartkowiak, Hans Ågren

J. Comput. Chem. 36, 1124-1131 (2015).
Received 30 October 2014; Revised 24 February 2015; Accepted 28 February 2015; Published online: 31 March 2015


In this study, we predict vibronic two-photon absorption (TPA) spectra for 4-nitroaniline in vacuo. The simulations are performed using density functional theory and the approximate second-order coupled-cluster singles and doubles model CC2. Thereby we also demonstrate the possibility of simulations of vibronic TPA spectra with ab initio wavefunction methods that include electron correlation for medium-sized systems. A special focus is put on the geometric derivatives of the second-order transition moment and the dipole moment difference between the charge-transfer excited state and the ground state. The results of CC2 calculations bring new insight into the vibronic coupling mechanism in TPA spectra of 4-nitroniline and demonstrate that the mixed term is quite large and that it also exhibits a negative interference with the Franck-Condon contribution. 2015 Wiley Periodicals, Inc.

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