Top Curr Chem (2016) 368: 347–376
DOI: 10.1007/128_2015_638
# Springer International Publishing Switzerland 2015
Published online: 24 May 2015
Computational Molecular Electronic
Spectroscopy with TD-DFT
Denis Jacquemin and Carlo Adamo
Abstract In this chapter we present applications of TD-DFT aiming at reproducing
and rationalizing the optical signatures of molecules, and, more precisely, the
absorption and fluorescence spectra of conjugated compounds belonging to both
organic and inorganic families. We particularly focus on the computations going
beyond the vertical approximation, i.e., on the calculation of 0–0 energies and
vibronic spectra with TD-DFT, and on large applications performed for “real-life”
structures (organic and inorganic dyes, optimization of charge-transfer structures,
rationalization of excited-state proton transfer, etc.). We present a series of recent
applications of TD-DFT methodology for these different aspects. The main conclusions of TD-DFT benchmarks aiming at pinpointing the most suited exchangecorrelation functionals are also discussed.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
2 Protocol to Determine the 0–0 Energies . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . 349
2.1 Gas Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
2.2 Condensed Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
2.3 Further Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3 Benchmarks . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . 355
D. Jacquemin (*)
CEISAM, UMR CNRS 6230, Universite ´ de Nantes, 2, rue de la Houssinie `re, 44322 Nantes,
France
Institut Universitaire de France, 103, blvd Saint-Michel, 75005 Paris, France
e-mail: Denis.Jacquemin@univ-nantes.fr
C. Adamo
IRCP UMR CNRS 8247, ENSCP-Chimie ParisTech, 11, rue Pierre et Marie Curie, 75005
Paris, France
Institut Universitaire de France, 103, blvd Saint-Michel, 75005 Paris, France
DOI: 10.1007/128_2015_638
# Springer International Publishing Switzerland 2015
Published online: 24 May 2015
Computational Molecular Electronic
Spectroscopy with TD-DFT
Denis Jacquemin and Carlo Adamo
Abstract In this chapter we present applications of TD-DFT aiming at reproducing
and rationalizing the optical signatures of molecules, and, more precisely, the
absorption and fluorescence spectra of conjugated compounds belonging to both
organic and inorganic families. We particularly focus on the computations going
beyond the vertical approximation, i.e., on the calculation of 0–0 energies and
vibronic spectra with TD-DFT, and on large applications performed for “real-life”
structures (organic and inorganic dyes, optimization of charge-transfer structures,
rationalization of excited-state proton transfer, etc.). We present a series of recent
applications of TD-DFT methodology for these different aspects. The main conclusions of TD-DFT benchmarks aiming at pinpointing the most suited exchangecorrelation functionals are also discussed.
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
2 Protocol to Determine the 0–0 Energies . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . 349
2.1 Gas Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
2.2 Condensed Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
2.3 Further Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
3 Benchmarks . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . 355
D. Jacquemin (*)
CEISAM, UMR CNRS 6230, Universite ´ de Nantes, 2, rue de la Houssinie `re, 44322 Nantes,
France
Institut Universitaire de France, 103, blvd Saint-Michel, 75005 Paris, France
e-mail: Denis.Jacquemin@univ-nantes.fr
C. Adamo
IRCP UMR CNRS 8247, ENSCP-Chimie ParisTech, 11, rue Pierre et Marie Curie, 75005
Paris, France
Institut Universitaire de France, 103, blvd Saint-Michel, 75005 Paris, France