High-order pump-probe and high-order two-dimensional electronic spectroscopy on the example of squaraine oligomers

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F23%3A10476126" target="_blank" >RIV/00216208:11320/23:10476126 - isvavai.cz</a>

Result on the web

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ymQ4mNzwDE" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ymQ4mNzwDE</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0139090" target="_blank" >10.1063/5.0139090</a>

Result language

angličtina

Original language name

High-order pump-probe and high-order two-dimensional electronic spectroscopy on the example of squaraine oligomers

Original language description

Time-resolved spectroscopy is commonly used to study diverse phenomena in chemistry, biology, and physics. Pump-probe experiments and coherent two-dimensional (2D) spectroscopy have resolved site-to-site energy transfer, visualized electronic couplings, and much more. In both techniques, the lowest-order signal, in a perturbative expansion of the polarization, is of third order in the electric field, which we call a one-quantum (1Q) signal because in 2D spectroscopy it oscillates in the coherence time with the excitation frequency. There is also a two-quantum (2Q) signal that oscillates in the coherence time at twice the fundamental frequency and is fifth order in the electric field. We demonstrate that the appearance of the 2Q signal guarantees that the 1Q signal is contaminated by non-negligible fifth-order interactions. We derive an analytical connection between an nQ signal and (2n + 1)th-order contaminations of an rQ (with r &lt; n) signal by studying Feynman diagrams of all contributions. We demonstrate that by performing partial integrations along the excitation axis in 2D spectra, we can obtain clean rQ signals free of higher-order artifacts. We exemplify the technique using optical 2D spectroscopy on squaraine oligomers, showing clean extraction of the third-order signal. We further demonstrate the analytical connection with higher-order pump-probe spectroscopy and compare both techniques experimentally. Our approach demonstrates the full power of higher-order pump-probe and 2D spectroscopy to investigate multi-particle interactions in coupled systems.

Czech name

—

Czech description

—

Type

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

CEP classification

—

OECD FORD branch

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2023

Confidentiality

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

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Volume of the periodical

158

Issue of the periodical within the volume

23

Country of publishing house

US - UNITED STATES

Number of pages

18

Pages from-to

234201

UT code for WoS article

001012235300001

EID of the result in the Scopus database

2-s2.0-85162967486