Linear and second-order nonlinear optical properties of ionic organic crystals

Tomasz Seidler, Katarzyna Stadnicka, Benoît Champagne

Research output: Contribution to journalArticle

Abstract

The linear and second-order nonlinear optical susceptibilities of three ionic organic crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), have been calculated by adopting a two-step multi-scale procedure, which consists in calculating: (i) the ion properties using ab initio or density functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order Møller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with experiment is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. The study has also demonstrated that including the dressing field leads to a decrease of the χ(2) response of ionic crystals whereas its effect is opposite for molecular crystals. Moreover, the results have also demonstrated that this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, it has been shown that the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities.

Original languageEnglish
Article number104109
JournalThe journal of chemical physics
Volume141
Issue number10
DOIs
Publication statusPublished - 2014

Fingerprint

Optical properties
ionic crystals
magnetic permeability
optical properties
Crystals
environment effects
crystals
Molecular crystals
electrostatics
dipoles
density functional theory
Density functional theory
Electrostatics
Ions
ions
Experiments
diethylaminosulfur trifluoride

Cite this

@article{28cbc96de546440c8cee3181c23e4778,
title = "Linear and second-order nonlinear optical properties of ionic organic crystals",
abstract = "The linear and second-order nonlinear optical susceptibilities of three ionic organic crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), have been calculated by adopting a two-step multi-scale procedure, which consists in calculating: (i) the ion properties using ab initio or density functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order M{\o}ller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with experiment is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. The study has also demonstrated that including the dressing field leads to a decrease of the χ(2) response of ionic crystals whereas its effect is opposite for molecular crystals. Moreover, the results have also demonstrated that this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, it has been shown that the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities.",
author = "Tomasz Seidler and Katarzyna Stadnicka and Beno{\^i}t Champagne",
year = "2014",
doi = "10.1063/1.4894483",
language = "English",
volume = "141",
journal = "The journal of chemical physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "10",

}

Linear and second-order nonlinear optical properties of ionic organic crystals. / Seidler, Tomasz; Stadnicka, Katarzyna; Champagne, Benoît.

In: The journal of chemical physics, Vol. 141, No. 10, 104109, 2014.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Linear and second-order nonlinear optical properties of ionic organic crystals

AU - Seidler, Tomasz

AU - Stadnicka, Katarzyna

AU - Champagne, Benoît

PY - 2014

Y1 - 2014

N2 - The linear and second-order nonlinear optical susceptibilities of three ionic organic crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), have been calculated by adopting a two-step multi-scale procedure, which consists in calculating: (i) the ion properties using ab initio or density functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order Møller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with experiment is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. The study has also demonstrated that including the dressing field leads to a decrease of the χ(2) response of ionic crystals whereas its effect is opposite for molecular crystals. Moreover, the results have also demonstrated that this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, it has been shown that the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities.

AB - The linear and second-order nonlinear optical susceptibilities of three ionic organic crystals, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and 4-N,N-dimethylamino-4'-N'-phenyl-stilbazolium hexafluorophosphate (DAPSH), have been calculated by adopting a two-step multi-scale procedure, which consists in calculating: (i) the ion properties using ab initio or density functional theory methods and then (ii) in accounting for the crystal environment effects using classical electrostatic models. Provided that the ionic properties are evaluated at the second-order Møller-Plesset level and that the dressing field effects using point charges are accounted for, the agreement with experiment is excellent and enables to explain the origin of the larger χ(2) response of DAPSH with respect to DAST and DSTMS. The study has also demonstrated that including the dressing field leads to a decrease of the χ(2) response of ionic crystals whereas its effect is opposite for molecular crystals. Moreover, the results have also demonstrated that this multi-scale approach can be used to interpret the impact of the nature and position of the counterion on the linear and nonlinear optical susceptibilities of ionic crystals. Finally, it has been shown that the use of a conventional exchange-correlation functional like B3LYP leads to severe overestimations of χ(1) but large underestimations of χ(2) whereas the use of homogeneous dipole field is not recommended because it usually leads to overestimations of the linear and nonlinear optical susceptibilities.

UR - http://www.scopus.com/inward/record.url?scp=84924225941&partnerID=8YFLogxK

U2 - 10.1063/1.4894483

DO - 10.1063/1.4894483

M3 - Article

C2 - 25217906

VL - 141

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

IS - 10

M1 - 104109

ER -