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A New Imaginary Term in the Second-Order Nonlinear Susceptibility from Charged Interfaces

Ma, Emily and Ohno, Paul E. and Kim, Jeongmin and Liu, Yangdongling and Lozier, Emilie H. and Miller, Thomas F., III and Wang, Hong-Fei and Geiger, Franz M. (2021) A New Imaginary Term in the Second-Order Nonlinear Susceptibility from Charged Interfaces. Journal of Physical Chemistry Letters, 12 (24). pp. 5649-5659. ISSN 1948-7185. doi:10.1021/acs.jpclett.1c01103. https://resolver.caltech.edu/CaltechAUTHORS:20210412-101224507

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Abstract

Nonresonant second harmonic generation (SHG) phase and amplitude measurements obtained from the silica–water interface at varying pH values and an ionic strength of 0.5 M point to the existence of a nonlinear susceptibility term, which we call χ_x^((3)), that is associated with a 90° phase shift. Including this contribution in a model for the total effective second-order nonlinear susceptibility produces reasonable point estimates for interfacial potentials and second-order nonlinear susceptibilities when χ_x^((3)) ≈ 1.5χ_(water)^((3)). A model without this term and containing only traditional χ^((2)) and χ^((3)) terms cannot recapitulate the experimental data. The new model also provides a demonstrated utility for distinguishing apparent differences in the second-order nonlinear susceptibility when the electrolyte is NaCl versus MgSO₄, pointing to the possibility of using heterodyne-detected SHG to investigate ion specificity in interfacial processes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.1c01103DOIArticle
https://doi.org/10.26434/chemrxiv.14378810.v1DOIDiscussion Paper
https://arxiv.org/abs/2104.02802arXivDiscussion Paper
ORCID:
AuthorORCID
Ohno, Paul E.0000-0003-4192-1888
Miller, Thomas F., III0000-0002-1882-5380
Wang, Hong-Fei0000-0001-8238-1641
Geiger, Franz M.0000-0001-8569-4045
Alternate Title:A New Imaginary Term in the 2nd Order Nonlinear Susceptibility from Charged Interfaces
Additional Information:© 2021 American Chemical Society. Received: April 6, 2021; Accepted: June 4, 2021; Published: June 10, 2021. P.E.O. gratefully acknowledges support from the National Science Foundation GRFP, the Schmidt Science Fellowship in partnership with the Rhodes Trust, and the Harvard University Center for the Environment. H.-F.W. gratefully acknowledges support from the National Natural Science Foundation of China (NSFC Grant 21727802). T.F.M. and F.M.G. gratefully acknowledge support from the California Institute of Technology and Northwestern University, respectively. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipUNSPECIFIED
Schmidt Science FellowshipUNSPECIFIED
Rhodes TrustUNSPECIFIED
Harvard UniversityUNSPECIFIED
National Natural Science Foundation of China21727802
CaltechUNSPECIFIED
Northwestern UniversityUNSPECIFIED
Issue or Number:24
DOI:10.1021/acs.jpclett.1c01103
Record Number:CaltechAUTHORS:20210412-101224507
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210412-101224507
Official Citation:A New Imaginary Term in the Second-Order Nonlinear Susceptibility from Charged Interfaces. Emily Ma, Paul E. Ohno, Jeongmin Kim, Yangdongling Liu, Emilie H. Lozier, Thomas F. Miller, Hong-Fei Wang, and Franz M. Geiger. The Journal of Physical Chemistry Letters 2021 12 (24), 5649-5659; DOI: 10.1021/acs.jpclett.1c01103
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108694
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:12 Apr 2021 17:41
Last Modified:06 Jul 2021 20:47

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