High-resolution Photoelectron Spectra Research Articles

Observation of Interatomic Coulombic Decay Induced by Double Excitation of Helium in Nanodroplets.

Interatomic Coulombic decay (ICD) plays a crucial role in weakly bound complexes exposed to intense or high-energy radiation. So far, neutral or ionic atoms or molecules have been prepared in singly excited electron or hole states that can transfer energy to neighboring centers and cause ionization and radiation damage. Here we demonstrate that a doubly excited atom, despite its extremely short lifetime, can decay by ICD; evidenced by high-resolution photoelectron spectra of He nanodroplets excited to the 2s2p+ state. We find that ICD proceeds by relaxation into excited He^{*}He^{+} atom-pair states, in agreement with calculations. The ability of inducing ICD by resonant excitation far above the single-ionization threshold opens opportunities for controlling radiation damage to a high degree of element specificity and spectral selectivity.

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0-13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy.

Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0-13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck-Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high-resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228±0.006 and 12.52±0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4 + fragment ions. The 0 K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i. e., AE0K(CH3CO+)=10.89±0.01 eV (including a reverse barrier of ~0.19 eV) and AE0K(CHO+)=11.54±0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

Photoionization of Nitrile-substituted Naphthalene and Benzene: Cation Spectroscopy, Photostability, and Implications for Photoelectric Gas Heating

We investigate the vacuum ultraviolet (VUV) photodynamics of gas phase 1- and 2-cyanonaphthalene and cyanobenzene, recently detected in the Taurus molecular cloud, by combining synchrotron radiation and a double imaging electron/ion coincidence setup. The high-resolution threshold photoelectron spectra (TPES) of all three molecules are obtained experimentally from which the adiabatic ionization energies are reported with very high accuracy, particularly for 2-cyanonaphthalene, for which no data exist at this level of precision. Theoretical calculations are performed to compare with the TPES for the ground electronic state of the cations. Furthermore, the different features observed in the extended TPES have been assigned to the different molecular orbitals with the help of the outer valence Green's function calculations. The present experiments also shed light on the kinetic energy distribution of the photoelectrons as a function of the incident photon energy, to describe their contribution to the photoelectric heating effect in the interstellar medium. In this context, we show how kinetic energy distributions can be obtained from our data for any given photon energy, such as the omnipresent Lyα line, or any given interstellar radiation field (ISRF). In addition, from the total ion yields, we estimate the photorates for a few ISRFs. Finally, we discuss the photodissociation of the two cyanonaphthalenes, quoting the activation energies of the dissociation channels with the help of Rice–Ramsperger–Kassel–Marcus modeling. It is observed that CN substitution does not cause any appreciable change to the VUV dissociative photoionization relaxation channel.

Spectroscopic observation of Feshbach resonances in the tellurium dimer anion.

We report on the high-resolution photodetachment spectroscopy of the cryogenically cooled anionic tellurium dimer (Te2-). The high-resolution resonant photoelectron spectrum yields an accurate electron affinity of 16 689.7(92) cm-1 or 2.0693(11) eV for Te2. Two resonant states of Te2- anions have been identified, positioned at 1092(17) cm-1 below and 250(11) cm-1 above the photodetachment threshold, respectively. The spectra of resonant two-photon detachment (R2PD) and autodetachment from a specific vibrational level through a Feshbach resonance exhibit notable non-Franck-Condon behaviors. Using the spectroscopic data from the current experiment, the equilibrium bond distances and spectroscopic constants of the ground state and two electronically excited states of Te2- were determined.

Deconvolution of the X-ray absorption spectrum of trans-1,3-butadiene with resonant Auger spectroscopy.

High-resolution carbon K-edge X-ray photoelectron, X-ray absorption, non-resonant and resonant Auger spectra are presented of gas phase trans-1,3-butadiene alongside a detailed theoretical analysis utilising nuclear ensemble approaches and vibronic models to simulate the spectroscopic observables. The resonant Auger spectra recorded across the first pre-edge band reveal a complex evolution of different electronic states which remain relatively well-localised on the edge or central carbon sites. The results demonstrate the sensitivity of the resonant Auger observables to the weighted contributions from multiple electronic states. The gradually evolving spectral features can be accurately and feasibly simulated within nuclear ensemble methods and interpreted with the population analysis.

Using 1,8-cineole plasma with both pulsed and continuous depositions to modify commercially available wound dressing materials.

The current clinical standards for infected chronic wounds are oral and topical antibiotics. These strategies are problematic because antibiotic resistance can occur with prolonged use. As an alternative to clinical methods, essential oils show promise in preventing bacterial growth. Specifically, 1,8-cineole-an active component in eucalyptus oil-exhibits antifungal, anti-inflammatory, and antibacterial properties. Applying 1,8-cineole directly onto a wound is challenging, however, due to its volatile nature. To combat this issue, plasma-enhanced chemical vapor deposition (PECVD) has been established as a method to deposit a stable 1,8-cineole-derived film on model surfaces (e.g., glass and electrospun polystyrene nanofibers). The current study represents an extension of previous work, where both pulsed and continuous 1,8-cineole plasmas were used to deposit a 1,8-cineole-derived film on two commercially available wound dressings. Three surface analyses were conducted to characterize the plasma-modified dressings. First, water contact angle goniometry data demonstrated a decrease in hydrofiber wettability after treatment. Through scanning electron spectroscopy, the surface morphology of both materials did not change upon treatment. When comparing pulsed and continuous treatments, deconvolution of high-resolution C1s x-ray photoelectron spectra showed no differences in functional group retention. Importantly, the chemical compositions of treated wound dressings were different compared to untreated materials. Overall, this work seeks to elucidate how different PECVD parameters affect the surface properties of wound dressings. Understanding these parameters represents a key step toward developing alternative chronic wound therapies.

Experimental and theoretical study of Cr(VI) photoreduction and adsorption onto SO42−-doped TiO2 obtained by plasma electrolytic oxidation

TiO2/SO42− surfaces obtained by plasma electrolytic oxidation were used for the reduction of Cr(VI) to Cr(III) present in wastewater, in order to study the behavior of TiO2/SO42− in Cr(VI) and Cr(III) ion adsorption by X-ray photoelectron spectroscopy and density functional theory calculations. High-resolution X-ray photoelectron spectra showed the presence of Cr(III) and Cr(VI) in the form of Cr(OH)3 and CrO42−, respectively. In the case of CrO42−, it was experimentally observed that once the surface is washed, they do not remain on it. In the case of Cr(OH)3, it does remain on the TiO2/SO42− surfaces. In order to validate the previous results, the interactions of Cr(VI) in the forms CrO42− and HCrO4− and Cr(III) in the forms Cr(OH)2+ and Cr(OH)3 were modeled by density functional theory +U on surfaces of: TiO2 without OH− groups (dry surfaces) and with OH− groups (wet surfaces) in addition to modeling on TiO2/SO42− surfaces without OH− groups (dry S-surfaces) and with OH− groups (wet S-surfaces). The results of the simulations showed that the presence of OH− on the surfaces with and without S atoms weakens the interaction of the surface with the Cr(VI). In the same way, the presence of superficial OH− energetically stabilizes Cr(III), compensating with the presence of OH− the formation of Cr(OH)3 and Cr(OH)2+ on the TiO2 surface with and without TiO2 atoms present. This results shed new light on the understanding of the reduction of Cr(VI) to Cr(III) on TiO2 surfaces and show how the surface plays an active role in the reduction of this contaminant.

High-Resolution Photoelectron Spectroscopy of Vibrationally Excited Vinoxide Anions.

High-resolution photoelectron spectra of vibrationally pre-excited vinoxide anions (CH2CHO-) are reported using the recently developed IR-cryo-SEVI technique. This method is combined with a newly developed implementation of vibrational perturbation theory that can readily identify relevant anharmonic couplings among nearly degenerate vibrational states. IR-cryo-SEVI spectra are obtained by resonant infrared excitation of vinoxide anions via the fundamental C-O (ν4, 1566 cm-1) or isolated C-H (ν3, 2540 cm-1) stretching vibrations prior to photodetachment. Excitation of the ν4 mode leads to a well-resolved photoelectron spectrum that is in excellent agreement with a harmonic Franck-Condon simulation. Excitation of the higher-energy ν3 mode results in a more complicated spectrum that requires consideration of the calculated anharmonic resonances in both the anion and the neutral. From this analysis, information about the zeroth-order states that contribute to the nominal ν3 wave function in the anion is obtained. In the neutral, we observe anharmonic splitting of the ν3 fundamental into a polyad feature with peaks at 2737(22), 2 835(18), and 2910(12) cm-1, for which only the center frequency has been previously reported. Overall, 9 of the 12 fundamental frequencies of the vinoxy radical are extracted from the IR-cryo-SEVI and ground-state cryo-SEVI spectra, most of which are consistent with previous measurements. However, we provide a new estimate of the ν5 (CH2 scissoring) fundamental frequency at 1395(11) cm-1 and attribute the discrepancy with previously reported values to a Fermi resonance with the 2ν11 overtone (CH2 wagging).

Benzimidazole-based covalent organic polymer nanosheets incorporated in mesoporous organosilica nanoparticles with excitation-dependent fluorescence for sensing of Cu2+

A novel type of small-sized nanosheets (TD-Si) was prepared by chemical exfoliating stacked bulk materials of benzimidazole-based covalent organic polymer (TpDAB). Then TD-Si was used as organosiloxane precursor to incorporate into silica frameworks of mesoporous organosilica nanoparticles (TD-MONs) using CTAB as structural-directing agents. The obtained TD-MONs show a clearly hexagonal mesoporous structure with high surface area. Moreover, the optical properties of TD-MONs were measured with fluorescence and Ultraviolet–visible (UV–vis) spectroscopies. The results showed that TD-MONs possessed excitation wavelength dependent fluorescence and had better fluorescence properties due to the reduction of π-π stacking between nano-layers of TpDAB polymer. The emission peaks of TD-MONs were red-shifted as the excitation wavelength increases and TD-MONs exhibited the optimal fluorescence emission at 525 nm when excited at 400 nm. TD-MONs showed high selectivity, sensitivity and recyclability toward copper ions and could be used for the detection of Cu2+ with a low limit of detection (LOD) as low as 3.77 × 10−7 M. In addition, the coordination interaction between TD-MONs and copper ions was demonstrated by FT-IR spectra and high-resolution X-ray photoelectron spectra, and further proved that the binding sites were carbonyl oxygen atoms and imidazole nitrogen atoms in TD-MONs. Therefore, TD-MONs is expected to be a high-sensitive chemical sensor for detecting Cu2+.

Strong configuration-interaction contributions to the angle-resolved 4p photoelectron spectra of atomic xenon

High-resolution photoelectron spectra of xenon (Xe) were measured in the $4p$ photoionization region. The anisotropy parameters \ensuremath{\beta} were obtained for several photoelectron peaks with angle-resolved photoelectron measurements. The various complicated spectral features were observed due to the perturbed $4{p}^{\ensuremath{-}1}$ spin-orbit doublet and adjacent satellite structures. An analysis based on a relativistic multiconfiguration calculation has been carried out. The key role of the strong interactions between the $4{p}^{\ensuremath{-}1}$ core hole and the $4{d}^{\ensuremath{-}2}nl$ configurations has been investigated in detail. Experimental peak energies and intensities are in good agreement with theory. We find that the many of the complicated features are $4{d}^{\ensuremath{-}2}nl$ satellite lines, and their intensities are determined mostly by the amount of $4{p}^{\ensuremath{-}1}$ configurations that are mixed in. The experimental \ensuremath{\beta} values agree quite well with theory, indicating that the photoelectron angular distributions are also strongly influenced by the $4p$ direct-ionization contributions.

Threshold Photoelectron Spectrum of the Phenoxy Radical.

The high-resolution photoion mass-selected threshold photoelectron spectrum (ms-TPES) of the phenoxy radical (C6H5O•), produced by pyrolysis of anisole, was investigated at the VUV beamline of the Swiss Light Source. Adiabatic ionization energies have been determined to be 8.56, 9.42, 9.76, and 9.94 eV to the X̃+1A1, ã+3A2, Ã+1A2, and b̃+3B2 cation states, respectively, supported by DFT, WFT, and composite-method calculations. A ring deformation mode was found to be active upon ionization by Franck-Condon analysis and responsible for the vibrational structure of the TPES in all four ion states. While the X̃+1A1 and ã+3A2 states' assignment agrees with the literature, we revise the energetic order of the Ã+1A2 and b̃+3B2 cation states in the ms-TPES, based on a pronounced lifetime broadening of the excited triplet state. This is rationalized by strong coupling between the triplet states as confirmed by EOM-EE-CCSD calculations indicating a conical intersection with a low-lying seam to the ã+3A2 state. Our study provides a well-resolved spectrum, to be used for the isomer-selective assignment of reactive species in combustion and catalysis and also serves as benchmark to evaluate theoretical methods to address closed- and open-shell singlet and triplet cation intermediates.

High Resolution Photoelectron Spectroscopy of the Acetyl Anion.

High-resolution photoelectron spectra of cryogenically cooled acetyl anions (CH3CO-) obtained using slow photoelectron velocity-map imaging are reported. The high resolution of the photoelectron spectrum yields a refined electron affinity of 0.4352 ± 0.0012 eV for the acetyl radical as well as the observation of a new vibronic structure that is assigned based on ab initio calculations. Three vibrational frequencies of the neutral radical are measured to be 1047 ± 3 cm-1 (ν6), 834 ± 2 cm-1 (ν7), and 471 ± 1 cm-1 (ν8). This work represents the first experimental measurement of the ν6 frequency of the neutral. The measured electron affinity is used to calculate a refined value of 1641.35 ± 0.42 kJ mol-1 for the gas-phase acidity of acetaldehyde. Analysis of the photoelectron angular distributions provides insight into the character of the highest occupied molecular orbital of the anion, revealing a molecular orbital with strong d-character. Additionally, details of a new centroiding algorithm based on finite differences, which has the potential to decrease data acquisition times by an order of magnitude at no cost to accuracy, are provided.

Modification of conventional peak shapes to accurately represent spectral asymmetry: High-Resolution X-ray photoelectron spectra of [C4C1Pyrr][NTf2] and [C8C1Im][NTf2] ionic liquids

X-ray photoelectron spectroscopy (XPS) is one of the most widely used techniques for surface characterization. Analysis of XPS data is challenging and requires the analyst to fit the data with synthetic line shapes to reach physically meaningful interpretations. Experimental spectral envelopes, however, are complex and display asymmetric features that are often ignored or attributed to additional chemical components. The high-resolution XPS spectra of [C4C1Pyrr][NTf2] and [C8C1Im][NTf2] all exhibit a degree of asymmetry which is systematically observed at the higher binding energy side of photoemission envelopes. We present the development of a refined fitting procedure for XPS spectra of these ionic liquid-based systems which include (a) Shirley background offset necessary to account for the insulator-like region and (b) spectral asymmetry in C 1s and N 1s regions. Further, Shirley and trapezoid components are applied to compensate for inelastic scattering taking place during electron transitions as high as 7.8 eV above the start of the fitting region in C 1s high-resolution spectrum. To demonstrate the fitness of this model, we present an analysis of a 2:1 mixture of [C4C1Pyrr][NTf2]: [C8C1Im][NTf2].

General time-dependent configuration-interaction singles. II. Atomic case

We present a specialization of the grid-based implementation of the time-dependent configuration-interaction singles described in the preceding paper (arXiv:2204.09966) to the case of spherical symmetry. We describe the intricate time propagator in detail, and conclude with a few example calculations. Among these, of note are high-resolution photoelectron spectra in the vicinity of the Fano resonances in photoionization of neon, and spin-polarized photoelectrons from xenon, in agreement with recent experiments.

Probing the Electronic Structure and Bond Dissociation of SO3 and SO3- Using High-Resolution Cryogenic Photoelectron Imaging.

The SO3 molecule and its radical anion SO3- are important chemical species atmospherically. However, their thermodynamic properties and electronic structures are not well known experimentally. Using cryogenically cooled anions, we have obtained high-resolution photoelectron images of SO3- and determined accurately the electron affinity (EA) of SO3 and the bond dissociation energy of SO3- → SO2 + O- for the first time. Because of the large geometry changes from the C3v SO3- to the D3h SO3, there is a negligible Franck-Condon factor (FCF) for the 0-0 detachment transition, that defines the EA of SO3. By fitting the high-resolution photoelectron spectra with computed FCFs using structures from high-level ab initio calculations, we have determined the EA of SO3 to be 2.126(6) eV. By monitoring the appearance of the O- signal in the photoelectron images at different photon energies, we are able to measure directly the bond dissociation energy of SO3-(X2A1) → SO2(X1A1) + O-(2P) to be 4.259 ± 0.006 eV, which also allow us to derive the dissociation energy for the spin-forbidden SO3(X1A1') → SO2(X1A1) + O(3P) to be 3.594(6) eV. The excited states of SO3- are calculated using high-level ab initio calculations, which are valuable in aiding the interpretation of autodetachment processes observed at various photon energies. The current study provides valuable information about the fundamental molecular properties of SO3, as well as the radical anion SO3-, which is known in redox reactions involving SO32- and may also play a role in the chemistry of SO2 in the atmosphere.

Oxygen incorporation in AlN films grown by plasma-enhanced atomic layer deposition

Oxygen is often detected as an impurity in III-nitride films deposited by atomic layer deposition (ALD). The presence of oxygen has deep and unfavorable influences on the structural and optical properties of AlN. We have studied the oxygen incorporation in AlN films prepared by hollow cathode plasma-assisted ALD by alternating H2 plasma. We report a decrease in the O concentration in the film upon the addition of H2 plasma flow. However, increasing the H2 plasma flow does not further decrease the O incorporation. Film composition became almost constant at the surface and beneath the surface of AlN films deposited using N2/H2 plasma. Only samples grown with N2/H2 plasma showed decreases in oxygen concentration from the surface to the bulk film. Oxygen produces important modifications in the structural, chemical, and electrical properties. The Al 2p, N 1s, and O 1s high-resolution x-ray photoelectron spectra represent that AlN films are composed of Al–N, Al–O, and N–Al–O bonds. X-ray photoelectron spectroscopy data suggest that the composition of the AlN film changes to AlON + AlN when N2 plasma is used. The valence band maximum position of the AlN film is found to be at ∼1.7 eV for oxygen atomic concentration ∼20 at. %. The TO and LO phonon modes are present in AlN films with oxygen contamination ∼20 at. % and disappear at high oxygen contamination (∼55 at. %).

Photoelectron spectroscopy of cryogenically cooled NiO2-via slow photoelectron velocity-map imaging.

High-resolution anion photoelectron spectra of cryogenically cooled NiO2- anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the X̃1Σg+ ← X̃2Πg, ã3Πg ← X̃2Πg, and Ã1Πg ← X̃2Πg photodetachment transitions of linear ONiO0/-, revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the ã3Πg and Ã1Πg states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO2 is obtained as well as precise term energies for the ã and à states of NiO2 of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck-Condon forbidden transitions involving the doubly degenerate ν2 bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.

Graphene oxide decorated with fullerenol nanoparticles for highly efficient removal of Pb(II) ions and ultrasensitive detection by total-reflection X-ray fluorescence spectrometry

• Superior nanoadsorbent for highly effective adsorption of Pb(II) ions. • Impressive adsorption capacity and selectivity of the adsorbent toward Pb(II). • Extremely small adsorbent dosage and very short adsorption time. • Very low detection limit of 2.3 pg mL −1 using a benchtop TXRF instrument. • Simple and accurate analysis of complex matrix samples. In this paper, the graphene oxide (GO) decorated with fullerenol nanoparticles C 60 (OH) 22 has been designed for the highly selective separation and ultrasensitive determination of lead ions. The grafting fullerenol nanoparticles to the surface of GO solves the problem of their high solubility in aqueous solutions and simultaneously uses their high hydrophilicity and deprotonation ability. The research has revealed unique adsorption properties of GO-C 60 (OH) 22 toward Pb(II) ions at pH 5.5, i.e., minimal adsorbent dose (5 mg L −1 ), impressive resistance to ionic strength (up to 1 mol L −1 ), and enormous adsorption capacity (1307 mg g −1 ), much higher than those of any of the currently reported sorbents. The adsorption isotherms, kinetics, and effect of ionic strength indicate that an inner-sphere model based on surface complexation is the main mechanism of Pb(II) adsorption on GO-C 60 (OH) 22 . The high-resolution O1s and Pb4f X-ray photoelectron spectra confirm the strong chelation of Pb(II) ions and suggest the various coordination of Pb(II) ions to the oxygen functional groups. The exceptional properties of GO-C 60 (OH) 22 , including the possibility of application in micro-quantities, were the basis for the development of the method for ultra-sensitive detection of Pb(II) ions using such micro-analytical technique as total-reflection X-ray fluorescence spectrometry (TXRF). The method allows obtaining an extremely low detection limit of 2.3 pg mL −1 using a low-power TXRF instrument. Due to the impressive selectivity of the method, the ultra-trace Pb(II) ions can be highly accurately determined in complex matrix samples, including high salinity waters challenging to analyze using other analytical techniques.

Interface engineering of Ni0.85Se/Ni3S2 nanostructure for highly enhanced hydrogen evolution in alkaline solution

Interface engineering is considered as an effective strategy to improve the hydrogen evolution reaction (HER) performance of electrocatalysts. Herein, the Ni0.85Se/Ni3S2 heterostructure grown on nickel foam (NF) is synthesized via successive wet-chemical processes. The obtained Ni0.85Se/Ni3S2 heterostructure is firstly investigated as an HER electrocatalyst in alkaline media and exhibits more excellent electrochemical properties over Ni3S2. And it delivers a low overpotential of 145 mV at a current density of −10 mA cm−2, and superior stability. Based on the analysis of high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectra (XPS), the enhanced HER activity is due to the modulation of surface electronic structure, ascribing from the construction of heterointerface between Ni0.85Se and Ni3S2. Meanwhile, the Ni0.85Se/Ni3S2 heterostructure prepared in this work is also verified to be employed as a promising alternative to noble metal catalysts in HER.

Adsorption characteristics of silver atoms and silver ions on silica surface in silver nanoparticle hydrosol system

Previous studies have demonstrated that silver ions (Ag+) can be released from silver nanoparticles (AgNPs) to produce a system of silver atoms (Ag0) and Ag+ in equilibrium, which may affect the environment through adsorption on sediment. Here, the adsorption behaviour of Ag0 and Ag+ in a AgNP hydrosol system on a silica surface was systematically investigated using experimental evaluation and first-principles calculations based on density functional theory. The adsorption environment and performance were first analysed by batch and fixed-bed experiments, which indicated that less adsorption occurred between silica and silver. Subsequent energy calculations and structural optimisation revealed that both Ag0 and Ag+ were more likely to be chemisorbed on the silica surface through covalent (AgO) bonds. The average adsorption energies of SiO2/Ag+ and SiO2/Ag0 were −5.445 and −3.61 eV, respectively. In addition, Ag0 lost an average of 0.86 electrons to the O4–silica bond. By contrast, only a few electrons, which bonded with O1, were transferred from silica to Ag+. Analyses of the density of states and crystal orbital Hamilton population revealed that O and Ag were hybridised with the 2p–4d orbitals after adsorption. In addition, the peak shifts in the high-resolution Ag 3d, O 1s and Si 2p X-ray photoelectron spectra after adsorption revealed changes in the chemical state. The presence of AgO bonds was confirmed by the surface-enhanced Raman scattering spectrum. Silica was selected as the main component of sediment in this study, and it is hoped that this work will motivate a simulation of the migration and transformation of silver by sediment in the water environment.