Hyperpolarizabilities of Push-Pull Chromophores in Solution: Interplay between Electronic and Vibrational Contributions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F22%3A73618761" target="_blank" >RIV/61989592:15640/22:73618761 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.mdpi.com/1420-3049/27/24/8738" target="_blank" >https://www.mdpi.com/1420-3049/27/24/8738</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.3390/molecules27248738" target="_blank" >10.3390/molecules27248738</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Hyperpolarizabilities of Push-Pull Chromophores in Solution: Interplay between Electronic and Vibrational Contributions

Popis výsledku v původním jazyce

Contemporary design of new organic non-linear optical (NLO) materials relies to a large extent on the understanding of molecular and electronic structure–property relationships revealed during the years by available computational approaches. The progress in theory—hand-in-hand with experiment—has enabled us to identify and analyze various physical aspects affecting the NLO responses, such as the environmental effects, molecular vibrations, frequency dispersion, and system dynamics. Although it is nowadays possible to reliably address these effects separately, the studies analyzing their mutual interplay are still very limited. Here, we employ density functional theory (DFT) methods in combination with an implicit solvent model to examine the solvent effects on the electronic and harmonic as well as anharmonic vibrational contributions to the static first hyperpolarizability of a series of push–pull (Formula presented.), (Formula presented.) -diphenylpolyene oligomers, which were experimentally shown to exhibit notable second-order NLO responses. We demonstrate that the magnitudes of both vibrational and electronic contributions being comparable in the gas phase significantly increase in solvents, and the enhancement can be, in some cases, as large as three- or even four-fold. The electrical and mechanical anharmonic contributions are not negligible but cancel each other out to a large extent. The computed dynamic solute NLO properties of the studied systems are shown to be in a fair agreement with those derived from experimentally measured electric-field-induced second-harmonic generation (EFISHG) signals. Our results substantiate the necessity to consider concomitantly both solvation and vibrational effects in modeling static NLO properties of solvated systems.

Název v anglickém jazyce

Hyperpolarizabilities of Push-Pull Chromophores in Solution: Interplay between Electronic and Vibrational Contributions

Popis výsledku anglicky

Contemporary design of new organic non-linear optical (NLO) materials relies to a large extent on the understanding of molecular and electronic structure–property relationships revealed during the years by available computational approaches. The progress in theory—hand-in-hand with experiment—has enabled us to identify and analyze various physical aspects affecting the NLO responses, such as the environmental effects, molecular vibrations, frequency dispersion, and system dynamics. Although it is nowadays possible to reliably address these effects separately, the studies analyzing their mutual interplay are still very limited. Here, we employ density functional theory (DFT) methods in combination with an implicit solvent model to examine the solvent effects on the electronic and harmonic as well as anharmonic vibrational contributions to the static first hyperpolarizability of a series of push–pull (Formula presented.), (Formula presented.) -diphenylpolyene oligomers, which were experimentally shown to exhibit notable second-order NLO responses. We demonstrate that the magnitudes of both vibrational and electronic contributions being comparable in the gas phase significantly increase in solvents, and the enhancement can be, in some cases, as large as three- or even four-fold. The electrical and mechanical anharmonic contributions are not negligible but cancel each other out to a large extent. The computed dynamic solute NLO properties of the studied systems are shown to be in a fair agreement with those derived from experimentally measured electric-field-induced second-harmonic generation (EFISHG) signals. Our results substantiate the necessity to consider concomitantly both solvation and vibrational effects in modeling static NLO properties of solvated systems.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

21002 - Nano-processes (applications on nano-scale); (biomaterials to be 2.9)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

MOLECULES

ISSN

1420-3049

e-ISSN

—

Svazek periodika

27

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

18

Strana od-do

"nečíslováno"

Kód UT WoS článku

000904358100001

EID výsledku v databázi Scopus

2-s2.0-85144866178