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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

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

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

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

Name of the periodical

MOLECULES

ISSN

1420-3049

e-ISSN

—

Volume of the periodical

27

Issue of the periodical within the volume

24

Country of publishing house

CH - SWITZERLAND

Number of pages

18

Pages from-to

"nečíslováno"

UT code for WoS article

000904358100001

EID of the result in the Scopus database

2-s2.0-85144866178