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Sum-frequency vibrational spectroscopy of centrosymmetric molecule at interfaces

Ren‐Hui Zheng, Wen‐Mei Wei, Shuocang Zhang

2023The Journal of Chemical Physics15 citationsDOI

Abstract

The centrosymmetric benzene molecule has zero first-order electric dipole hyperpolarizability, which results in no sum-frequency vibrational spectroscopy (SFVS) signal at interfaces, but it shows very strong SFVS experimentally. We perform a theoretical study on its SFVS, which is in good agreement with the experimental results. Its strong SFVS mainly comes from the interfacial electric quadrupole hyperpolarizability rather than the symmetry-breaking electric dipole, bulk electric quadrupole, and interfacial and bulk magnetic dipole hyperpolarizabilities, which provides a novel and completely unconventional point of view.

Topics & Concepts

HyperpolarizabilityQuadrupoleDipoleSpectroscopyChemistryElectric dipole momentMolecular physicsAtomic physicsMoleculeComputational chemistryPhysicsPolarizabilityQuantum mechanicsOrganic chemistrySpectroscopy and Quantum Chemical StudiesSolid-state spectroscopy and crystallographyNonlinear Optical Materials Research