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  4. Size dependence of second-harmonic scattering from nanoparticles: Disentangling surface and electrostatic contributions
 
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research article

Size dependence of second-harmonic scattering from nanoparticles: Disentangling surface and electrostatic contributions

Chu, Bingxin  
•
Marchioro, Arianna  
•
Roke, Sylvie  
March 7, 2023
Journal Of Chemical Physics

Polarimetric angle-resolved second-harmonic scattering (AR-SHS) is an all-optical tool enabling the study of unlabeled interfaces of nano-sized particles in an aqueous solution. As the second harmonic signal is modulated by interference between nonlinear contributions originating at the particle's surface and those originating in the bulk electrolyte solution due to the presence of a surface electrostatic field, the AR-SHS patterns give insight into the structure of the electrical double layer. The mathematical framework of AR-SHS has been previously established, in particular regarding changes in probing depth with ionic strength. However, other experimental factors may influence the AR-SHS patterns. Here, we calculate the size dependence of the surface and electrostatic geometric form factors for nonlinear scattering, together with their relative contribution to the AR-SHS patterns. We show that the electrostatic term is stronger in the forward scattering direction for smaller particle sizes, while the ratio of the electrostatic to surface terms decreases with increasing size. Besides this competing effect, the total AR-SHS signal intensity is also weighted by the particle's surface characteristics, given by the surface potential phi(0) and the second-order surface susceptibility chi((2))(s,2). The weighting effect is experimentally demonstrated by comparing SiO2 particles of different sizes in NaCl and NaOH solutions of varying ionic strengths. For NaOH, the larger chi((2))(s,2) values generated by deprotonation of surface silanol groups prevail over the electrostatic screening occurring at high ionic strengths; however, only for larger particle sizes. This study establishes a better connection between the AR-SHS patterns and surface properties and predicts trends for arbitrarily-sized particles.

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Type
research article
DOI
10.1063/5.0135157
Web of Science ID

WOS:000943244300005

Author(s)
Chu, Bingxin  
•
Marchioro, Arianna  
•
Roke, Sylvie  
Date Issued

2023-03-07

Publisher

AIP Publishing

Published in
Journal Of Chemical Physics
Volume

158

Issue

9

Article Number

094711

Subjects

Chemistry, Physical

•

Physics, Atomic, Molecular & Chemical

•

Chemistry

•

Physics

•

interfacial water-molecules

•

particle-size

•

label-free

•

colloidal particles

•

charged interface

•

generation

•

transport

•

polarization

•

membranes

•

model

Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LBP  
Available on Infoscience
May 8, 2023
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/197308
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