Electronic Structure of Liquid Alkanes: A Representative Case of Liquid Hexanes and Cyclohexane Studied Using Polarization-Dependent Two-Photon Absorption Spectroscopy

Two-photon absorption (2PA) spectra of liquid cyclohexane and hexanes are reported for the energy range 6.4–8.5 eV (177–145 nm), providing detailed information about their electronic structures in bulk liquid. Using a broadband pump–probe fashion, we measured the continuous 2PA spectra by simultaneous absorption of a 266 nm (4.6 eV) pump photon and one UV–vis probe photon from the white-light continuum (1.8–3.9 eV). Theoretical one-photon absorption (1PA) and 2PA cross sections of isolated gas phase molecules are computed by the equation of motion coupled-cluster method with single and double substitutions (EOM-CCSD) to substantiate the assignment of the experimental spectra, and the natural transition orbital (NTO) analysis provides visualization of the participating orbitals in a transition. Our analysis suggests that upon solvation transitions at the lowest excitation energy involving promotion of electron to the 3s Rydberg orbitals are blue-shifted (∼0.55 eV for cyclohexane and ∼0.18 eV for hexanes) to a greater extent as compared to those involving other Rydberg orbitals, which is similar to the behavior observed for water and alcohols. All other transitions experience negligible (cyclohexane) or minor red-shift by ∼0.15-0.2 eV (hexane) upon solvation. In both alkanes, the spectra are entirely dominated by Rydberg transitions: the most intense bands in 1PA and 2PA spectra are due to the excitation of electrons to the Rydberg “p” and “d” type orbitals, respectively, although one transition terminating in the 3s Rydberg has significant 2PA strength. This work demonstrates that the gas phase electronic transition properties in alkanes are not significantly altered upon solvation. In addition, electronic structure calculations using an isolated-molecule framework appear to provide a reasonable starting point for a semiquantitative picture for spectral assignment and also to analyze the solvatochromic shifts for liquid phase absorption spectra

Electronic Structure of Liquid Methanol and Ethanol from Polarization-Dependent Two-Photon Absorption Spectroscopy

Two-photon absorption (2PA) spectra of liquid methanol and ethanol are reported for the energy range 7–10 eV from the first electronic excitation to close to the liquid-phase ionization potential. The spectra give detailed information on the electronic structures of these alcohols in the bulk liquid. The focus of this Article is to examine the electronic structure change compared with water on substitution of a hydrogen by an alkyl group. Continuous 2PA spectra are recorded in the broadband pump–probe fashion, with a fixed pump pulse in the UV region and a white-light continuum as a probe. Pump pulses of two different energies, 4.6 and 6.2 eV, are used to cover the spectral range up to 10 eV. In addition, theoretical 2PA cross sections for both molecules isolated in the gas phase are computed by the equation-of-motion coupled-cluster method with single and double substitutions (EOM-CCSD). These computational results are used to assign both the experimental 2PA and literature one-photon linear absorption spectra. The most intense spectral features are due to transitions to the Rydberg states, and the 2PA spectra are dominated by the totally symmetric 3pz ← 2pz transition in both alcohols. The experimental 2PA spectra are compared with the simulated 2PA spectra based on ab initio calculations that reveal a general blue shift of the excited transitions upon solvation. The effective 2PA thresholds in methanol and ethanol decrease to 6.9 eV compared with 7.8 eV for water. The analysis of the 2PA polarization ratio leads us to conclude that the excited states of ethanol deviate more markedly from water in the lower energy region compared with methanol. The polarization dependence of the 2PA spectra reveal the symmetries of the excited states within the measured energy range. Natural transition orbital calculations are performed to visualize the nature of the transitions and the orbitals participating during electronic excitation

Vibrational Sum Frequency Generation Spectroscopy Measurement of the Rotational Barrier of Methyl Groups on Methyl-Terminated Silicon(111) Surfaces

The methyl-terminated Si(111) surface possesses a 3-fold in-plane symmetry, with the methyl groups oriented perpendicular to the substrate. The propeller-like rotation of the methyl groups is hindered at room temperature and proceeds via 120° jumps between three isoenergetic minima in registry with the crystalline Si substrate. We have used line-shape analysis of polarization-selected vibrational sum frequency generation spectroscopy to determine the rotational relaxation rate of the surface methyl groups and have measured the temperature dependence of the relaxation rate between 20 and 120 °C. By fitting the measured rate to an Arrhenius dependence, we extracted an activation energy (the rotational barrier) of 830 ± 360 cm–1 and an attempt frequency of (2.9 ± 4.2) × 1013 s–1 for the methyl rotation process. Comparison with the harmonic frequency of a methyl group in a 3-fold cosine potential suggests that the hindered rotation occurs via uncorrelated jumps of single methyl groups rather than concerted gear-like rotation

Unlocking the Facet-Dependent Ligand Exchange on Rutile TiO₂ of a Rhenium Bipyridyl Catalyst for CO₂ Reduction

Covalent attachment of molecular catalysts to electrode surfaces is an attractive approach to develop robust catalytic materials. Selectivity and tunability of the resulting catalytic surface can be achieved by ligand design, making surface-attached CO2 catalysts of immense interest for zero carbon technologies. Unfortunately, the functionality of heterogenized catalysts strongly depends on the nature of the electrode surface and the specific binding mode of the catalyst on the electrode surface. Here, we perform experimental and theoretical vibrational sum-frequency generation spectroscopy (VSFG) to investigate the binding configuration of a popular molecular CO2 reduction catalyst, the Re(dcbpy)(CO)3Cl (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) complex (ReC0A), heterogenized on a 0.5% niobium (Nb)-doped rutile TiO2 (100) crystal. We find evidence of ligand exchange induced upon binding to the (100) TiO2 facet that was not observed on other TiO2 facets. The structural changes are induced by the sawtooth morphology of the TiO2 (100) facet, establishing interactions that lead to chloride (Cl–) ligand exchange with hydroxide (OH–) and formation of the Re(dcbpy)(CO)3OH (ReOH) adsorbate. DFT calculations show bidentate binding of ReOH through its carboxylate (COO–) groups in a flat-lying orientation stabilized by hydrogen-bonding of the OH– proton to the TiO2 surface. The OH-substituted site interacts strongly with the (100) TiO2 surface in a configuration unfavorable for the CO2 exchange that is necessary for catalytic functionality. These findings provide evidence of facet-dependent changes of the heterogenized molecular catalyst, underscoring the critical role of the surface facet while designing electrocatalytic materials

Sub-Nanometer Mapping of the Interfacial Electric Field Profile Using a Vibrational Stark Shift Ruler

The characterization of electrical double layers is important since the interfacial electric field and electrolyte environment directly affect the reaction mechanisms and catalytic rates of electrochemical processes. In this work, we introduce a spectroscopic method based on a Stark shift ruler that enables mapping the electric field strength across the electric double layer of electrode/electrolyte interfaces. We use the tungsten-pentacarbonyl­(1,4-phenelenediisocyanide) complex attached to the gold surface as a molecular ruler. The carbonyl (CO) and isocyanide (NC) groups of the self-assembled monolayer (SAM) provide multiple vibrational reporters situated at different distances from the electrode. Measurements of Stark shifts under operando electrochemical conditions and direct comparisons to density functional theory (DFT) simulations reveal distance-dependent electric field strength from the electrode surface. This electric field profile can be described by the Gouy–Chapman–Stern model with Stern layer thickness of ∼4.5 Å, indicating substantial solvent and electrolyte penetration within the SAM. Significant electro-induction effect is observed on the W center that is ∼1.2 nm away from the surface despite rapid decay of the electric field (∼90%) within 1 nm. The applied methodology and reported findings should be particularly valuable for the characterization of a wide range of microenvironments surrounding molecular electrocatalysts at electrode interfaces and the positioning of electrocatalysts at specific distances from the electrode surface for optimal functionality

Field-Dependent Orientation and Free Energy of D₂O at an Electrode Surface Observed via SFG Spectroscopy

Polarization-selected vibrational sum frequency generation (SFG) spectroscopy of D2O is used to obtain the orientation of the free OD bond at a monolayer graphene electrode. We modulate the interfacial field by varying the applied electrochemical potential, and we measure the resulting change in the orientation. A hyperpolarizability model is used for the orientational analysis, which assumes a quadratic free energy orienting potential in the absence of the field, whose minimum and curvature determine the average tilt angle and the Gaussian width of the orientational distribution. The average free OD tilt angle changes in an approximately linear fashion with the applied field, from 46° from normal at −0.9 V vs Ag/AgCl (E = −0.02 V/Å) to 32° at −3.9 V vs Ag/AgCl (E = −0.17 V/Å). Using this approach, we map the free energy profile for the molecular orientation of interfacial water by measuring the reversible response to an external perturbation, i.e., a torque applied by an electric field acting on the molecule’s permanent dipole moment. This allows us to extract the curvature of the free energy orienting potential of interfacial water, which is (4.0 ± 0.8) × 10–20 J/rad2 (or 0.25 ± 0.05 eV/rad2 )

Molecular Orientation of Poly-3-hexylthiophene at the Buried Interface with Fullerene

Molecular orientation at the donor–acceptor interface plays a crucial role in determining the efficiency of organic semiconductor materials. We have used vibrational sum frequency generation spectroscopy to determine the orientation of poly-3-hexylthiophene (P3HT) at the planar buried interface with fullerene (C60). The thiophene rings of P3HT have been found to tilt significantly toward C60, making an average angle θ ≈ 49° ± 10° between the plane of the ring and the interface. Such tilt may be attributed to π–π stacking interactions between P3HT and C60 and may facilitate efficient charge transfer between donor and acceptor. Upon annealing, the thiophene rings tilt away from the interface by Δθ = 12–19°. This may be attributed to higher crystallinity of annealed P3HT that propagates all the way to the interface, resulting in more “edge-on” orientation, which is consistent with the observed red-shift by ∼6 cm–1 and spectral narrowing of the C=C stretch bands