title: Excited State Geometries and Vertical Emission Energies of Solvated Dyes for DSSC: A PCM/TD-DFT Benchmark Study.
abstract: The ability of Time-Dependent Density Functional Theory (TD-DFT) to provide excited state geometries and reproduce emission energies of organic D-π-A dyes designed for DSSC applications is evaluated. The performance of six functionals (CAM-B3LYP, MPW1K, ωB97X-D, LC-BLYP, LC-ωPBE, and M06-HF) in combination with three basis sets (cc-pVDZ, 6-31+G(d,p), and 6-311+G(2d,p)) has been analyzed. Solvent effects have been taken into account by means of a Polarizable Continuum Model in both LR and SS formalisms. Our LR-PCM/TD-DFT results show that accurate emission energies are obtained only when solvent effects are included in the computation of excited state geometries and when a range separated hybrid functional is used. Vertical emission energies are reproduced with a mean absolute error of at most 0.2 eV. The accuracy is further improved using the SS-PCM formalism.
authors.affiliation: Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.|CSGI, Consorzio per lo Sviluppo dei Sistemi a Grande Interfase, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Caterina
authors.initials: C
authors.lastname: Bernini
authors.affiliation: CNR - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Zani
authors.affiliation: CNR - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Massimo
authors.initials: M
authors.lastname: Calamante
authors.affiliation: CNR - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Gianna
authors.initials: G
authors.lastname: Reginato
authors.affiliation: CNR - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Mordini
authors.affiliation: Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Taddei
authors.affiliation: Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.|CSGI, Consorzio per lo Sviluppo dei Sistemi a Grande Interfase, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Riccardo
authors.initials: R
authors.lastname: Basosi
authors.affiliation: Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.|CSGI, Consorzio per lo Sviluppo dei Sistemi a Grande Interfase, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence, Italy.
authors.forename: Adalgisa
authors.initials: A
authors.lastname: Sinicropi