Quantum Chemical Methods for Predicting and Interpreting Second-Order Nonlinear Optical Properties: from Small to Extended π-Conjugated Molecules

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Résumé

This chapter addresses the methodological and computational aspects related to the prediction of molecular second-order nonlinear optical properties, i.e., the first hyperpolarizability (β), by using quantum chemistry methods. Both small (reference) molecules and extended push-pull π-conjugated systems are considered, highlighting contrasted effects about (i) the choice of a reliable basis set together with the convergence of β values as a function of the basis set size, (ii) the amplitude of electron correlation contributions and its estimate using wave function and density functional theory methods, (iii) the description of solvent effects using implicit and explicit solvation models, (iv) frequency dispersion effects in off-resonance conditions, and (v) numerical accuracy issues. When possible, comparisons with experiment are made. All in all, these results demonstrate that the calculations of β remain a challenge and that many issues need to be carefully addressed, pointing out difficulties toward elaborating black-box and computationally cheap protocols. Still, several strategies can be designed in order to achieve a targeted accuracy, either for reference molecules displaying small β responses or for molecules presenting large β values and a potential in optoelectronics and photonics.
langue originaleAnglais
Pages (de - à)117-138
Nombre de pages21
journalFrontiers in Quantum Chemistry
étatPublié - 2018

Empreinte digitale

Optical properties
optical properties
Molecules
molecules
Quantum chemistry
Electron correlations
Solvation
quantum chemistry
Wave functions
Optoelectronic devices
Photonics
Density functional theory
solvation
boxes
wave functions
photonics
density functional theory
estimates
predictions
electrons

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title = "Quantum Chemical Methods for Predicting and Interpreting Second-Order Nonlinear Optical Properties: from Small to Extended π-Conjugated Molecules",
abstract = "This chapter addresses the methodological and computational aspects related to the prediction of molecular second-order nonlinear optical properties, i.e., the first hyperpolarizability (β), by using quantum chemistry methods. Both small (reference) molecules and extended push-pull π-conjugated systems are considered, highlighting contrasted effects about (i) the choice of a reliable basis set together with the convergence of β values as a function of the basis set size, (ii) the amplitude of electron correlation contributions and its estimate using wave function and density functional theory methods, (iii) the description of solvent effects using implicit and explicit solvation models, (iv) frequency dispersion effects in off-resonance conditions, and (v) numerical accuracy issues. When possible, comparisons with experiment are made. All in all, these results demonstrate that the calculations of β remain a challenge and that many issues need to be carefully addressed, pointing out difficulties toward elaborating black-box and computationally cheap protocols. Still, several strategies can be designed in order to achieve a targeted accuracy, either for reference molecules displaying small β responses or for molecules presenting large β values and a potential in optoelectronics and photonics.",
author = "Beno{\^i}t Champagne and Pierre Beaujean and {De Wergifosse}, Marc and {Hidalgo Cardenuto}, Marcelo and Vincent Li{\'e}geois and Fr{\'e}d{\'e}ric Castet",
year = "2018",
language = "English",
pages = "117--138",
journal = "Advances in Quantum Chemistry",
issn = "0065-3276",
publisher = "Academic Press Inc.",

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TY - JOUR

T1 - Quantum Chemical Methods for Predicting and Interpreting Second-Order Nonlinear Optical Properties

T2 - from Small to Extended π-Conjugated Molecules

AU - Champagne, Benoît

AU - Beaujean, Pierre

AU - De Wergifosse, Marc

AU - Hidalgo Cardenuto, Marcelo

AU - Liégeois, Vincent

AU - Castet, Frédéric

PY - 2018

Y1 - 2018

N2 - This chapter addresses the methodological and computational aspects related to the prediction of molecular second-order nonlinear optical properties, i.e., the first hyperpolarizability (β), by using quantum chemistry methods. Both small (reference) molecules and extended push-pull π-conjugated systems are considered, highlighting contrasted effects about (i) the choice of a reliable basis set together with the convergence of β values as a function of the basis set size, (ii) the amplitude of electron correlation contributions and its estimate using wave function and density functional theory methods, (iii) the description of solvent effects using implicit and explicit solvation models, (iv) frequency dispersion effects in off-resonance conditions, and (v) numerical accuracy issues. When possible, comparisons with experiment are made. All in all, these results demonstrate that the calculations of β remain a challenge and that many issues need to be carefully addressed, pointing out difficulties toward elaborating black-box and computationally cheap protocols. Still, several strategies can be designed in order to achieve a targeted accuracy, either for reference molecules displaying small β responses or for molecules presenting large β values and a potential in optoelectronics and photonics.

AB - This chapter addresses the methodological and computational aspects related to the prediction of molecular second-order nonlinear optical properties, i.e., the first hyperpolarizability (β), by using quantum chemistry methods. Both small (reference) molecules and extended push-pull π-conjugated systems are considered, highlighting contrasted effects about (i) the choice of a reliable basis set together with the convergence of β values as a function of the basis set size, (ii) the amplitude of electron correlation contributions and its estimate using wave function and density functional theory methods, (iii) the description of solvent effects using implicit and explicit solvation models, (iv) frequency dispersion effects in off-resonance conditions, and (v) numerical accuracy issues. When possible, comparisons with experiment are made. All in all, these results demonstrate that the calculations of β remain a challenge and that many issues need to be carefully addressed, pointing out difficulties toward elaborating black-box and computationally cheap protocols. Still, several strategies can be designed in order to achieve a targeted accuracy, either for reference molecules displaying small β responses or for molecules presenting large β values and a potential in optoelectronics and photonics.

M3 - Article

SP - 117

EP - 138

JO - Advances in Quantum Chemistry

JF - Advances in Quantum Chemistry

SN - 0065-3276

ER -