Two-dimensional electronic–vibrational sum frequency spectroscopy for interactions of electronic and nuclear motions at interfaces

Interactions of electronic and vibrational degrees of freedom are essential for understanding excited-states relaxation pathways of molecular systems at interfaces and surfaces. Here, we present the development of interface-specific two-dimensional electronic–vibrational sum frequency generation (2D-EVSFG) spectroscopy for electronic–vibrational couplings for excited states at interfaces and surfaces. We demonstrate this 2D-EVSFG technique by investigating photoexcited interface-active (E)-4-((4-(dihexylamino) phenyl)diazinyl)-1-methylpyridin-1- lum (AP3) molecules at the air–water interface as an example. Our 2D-EVSFG experiments show strong vibronic couplings of interfacial AP3 molecules upon photoexcitation and subsequent relaxation of a locally excited (LE) state. Time-dependent 2D-EVSFG experiments indicate that the relaxation of the LE state, S2, is strongly coupled with two high-frequency modes of 1,529.1 and 1,568.1 cm−1. Quantum chemistry calculations further verify that the strong vibronic couplings of the two vibrations promote the transition from the S2 state to the lower excited state S1. We believe that this development of 2D-EVSFG opens up an avenue of understanding excited-state dynamics related to interfaces and surfaces.

Structure of the Silica/Divalent Electrolyte Interface: Molecular Insight into Charge Inversion with Increasing pH

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl₂ electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm^-1. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca²⁺ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.

Structure of the Silica/Divalent Electrolyte Interface: Molecular Insight into Charge Inversion with Increasing pH

The molecular origin of overcharging at mineral oxide surfaces remains a cause of contention within the geochemistry, physics, and colloidal chemistry communities owing to competing “chemical” vs “physical” interpretations. Here, we combine vibrational sum frequency spectroscopy and streaming potential measurements to obtain molecular and macroscopic insights into the pH-dependent interactions of calcium ions with a fused silica surface. In 100 mM CaCl₂ electrolyte, we observe evidence of charge neutralization at pH~10.5, as deducted from a minimum in the interfacial water signal. Concurrently, adsorption of calcium hydroxide cations is inferred from the appearance of a spectral feature at ~3610 cm^-1. However, the interfacial water signal increases at higher pH, while adsorbed calcium hydroxide appears to remain constant, indicating that overcharging results from hydrated Ca²⁺ ions present within the Stern layer. These findings suggest that both specific adsorption of hydrolyzed ions and ion-ion correlations of hydrated ions govern silica overcharging with increasing pH.

Identifying Eigen-like hydrated protons at negatively charged interfaces

Despite the importance of the hydrogen ion in a wide range of biological, chemical, and physical processes, its molecular structure in solution remains lively debated. Progress has been primarily hampered by the extreme diffuse nature of the vibrational signatures of hydrated protons in bulk solution. Using the inherently surface-specific vibrational sum frequency spectroscopy technique, we show that at selected negatively charged interfaces, a resolved spectral feature directly linked to the H3O+ core in an Eigen-like species can be readily identified in a biologically compatible pH range. Centered at ~2540 cm−1, the band is seen to shift to ~1875 cm−1 when forming D3O+ upon isotopic substitution. The results offer the possibility of tracking and understanding from a molecular perspective the behavior of hydrated protons at charged interfaces.

Preferred orientations of organic cations at lead-halide perovskite interfaces revealed using vibrational sum-frequency spectroscopy

Using vibrational sum frequency generation (VSFG) spectroscopy, we investigate the behaviour of organic cations at the surface of a series of multilayer lead halide perovskite systems, finding that the behaviour of the organic cations changes dramatically close to the interface.

Identifying Eigen-Like Hydrated Protons at Negatively Charged Interfaces

Despite the importance of the hydrogen ion in a wide range of biological, chemical, and physical processes, its molecular structure in solution remains lively debated. Progress has been primarily hampered by the extreme diffuse nature of the vibrational signatures of hydrated protons in bulk solution. Using the inherently surface-specific vibrational sum frequency spectroscopy, we show that at selected negatively charged interfaces, a resolved spectral feature directly linked to the H₃O⁺ core in an Eigen-like species can be readily identified in a biologically compatible pH range. The results offer a new molecular perspective for tracking and understanding the behaviour of hydrated protons at interfaces.