Coordination of acetonitrile (CH3CN) to platinum (111): Evidence for an η2(C,N) species

Acetonitrile (CH₃CN) coordination to a Pt(111) surface has been studied with electron energy loss vibrational spectroscopy (EELS), XPS, thermal desorption and work function measurements. We compare data for the surface states with known acetonitrile coordination complexes. For CH₃CN adsorbed on Pt(111) at 100 K, the molecule is rehybridized and adsorbs with the CN bond parallel or slightly inclined to the surface plane in an η²(C, N) configuration. The ν(CN) frequency is 1615 cm^?1 and the C ls and N ls binding energies are 284.6 eV and 397.2 eV respectively. By contrast, weakly adsorbed multilayer acetonitrile exhibits a ν(CN) vibrational frequency of 2270 cm^?1, and C ls and N ls binding energies of 286.9 eV and 400.1 eV respectively. Both the EELS and XPS results are consistent with rehybridization of the CN triple bond to a double bond with both C and N atoms of the CN group attached to the surface. In addition to this majority η²(C, N) monolayer state, evidence is found for a second, more strongly bound minority molecular state in thermal desorption spectra. As a result of the low coverage of this state, EELS was unable to spectroscopically identify it and we tentatively assign it as an η⁴(C, N) species associated with accidental step sites. By contrast to the surface complexes, almost all of the known platinum-nitrile coordination complexes are end-bonded via the N lone-pair orbital. Several cases of side-on bonding are known, however, and we compare the results with the known complex Fe₃(η²-NCCH₃)(CO)₉. The difference in the coordinative properties of a Pt(111) surface versus a single Pt atom must be due to the increased ability of multi-atom arrays to back-donate electrons into the π¹ system of acetonitrile. Previously published EELS and XPS results for monolayer acetonitrile on Ni(111) and polycrystalline films are almost identical to the present results on Pt(111). We believe that the monolayer of $\text{CH}{}_3\text{CN}\text{Ni}\text{(111)}$ is also an η²(C, N) species, not an end-bonded species previously proposed by Friend, Muetterties and Gland.     

Vibrational spectra of ethylene and acetylene on metal surfaces - an electron energy loss study of ethylene adsorbed on Ni(110) and its carbided surface,and the use of metal-cluster analogies

An analysis has been made of on- and off-specular electron energy loss spectra (EELS) from C₂H₄ and C₂D₄ adsorbed on a clean Ni(110) and also a carbided Ni(110) surface. The carbided surface was prepared by heating the clean Ni surface in ethylene to 573 K or above. EELS spectra were obtained using a Leybold-Heraeus spectrometer at a beam energy of 3.0 eV and with a resolution of ca. 6.5 meV (ca. 50 cm^?1).The loss spectrum from ethylene at low temperatures (110 K) showed principal features at 3000 (w), 1468 (w), 1162 (s), 879 (w) and 403 cm^?1 (s) (C₂D₄ adsorption) and 2186 (w), 1258 (ms), 944 (ms), 645 (w) and 400 cm^?1 (s) (C₂D₄ adsorption). The overall pattern of wavenumbers and intensifies of the C₂H₄/C₂D₄ loss peaks is very similar in form (although systematically different in positions) to those previously observed on Ni(111) (ref.1) and Pt(111) (ref.2) surfaces at low temperatures. Like these earlier spectra,the EELS results for C₂H₄/C₂D₄ adsorbed on clean Ni(110) can be well interpreted in terms of a MCH₂CH₂M/MCD₂CD₂M species (M = metal) with the CC bond parallel to the surface.After adsorption on the carbided Ni(110) surfaces at 125 K,the main loss features occur at 3065 (m), 2992 (m), 1524 (ms), 1250 (s), 895 (s), and 314 cm^?1 (vs) (C₂H₄ adsorption) and 2339 (m), 2242 (m), 1395 (s), 968 (s), 661 (m) and 314 cm^?1 (vs). With the exceptions of reduced intensities of the bands at 895 cm^?1 (C₂H₄) and 661 cm^?1 (C₂D₄) this pattern of losses - particularly the 1550-1200 cm^?1 features which can be assigned to coupled νCC and δCH₂/δCD₂ modes - is well related to similar results on Cu(100) (ref.3) and Pd(111) (ref.4) which have been interpreted convincingly in terms of the presence of π-bonded species, (C₂H₄)M or (C₂D₄)M on the surface. This structural assignment is supported by comparison with the vibrational spectra of Zeise's salt, K[PtCl₃(C₂H₄)].H₂O (refs.5&6).Spectral changes occur on warming C₂H₄ on the clean Ni(110) surface with a growth of a feature near 895 cm^?1 at 200 K. At 300 K a rather poorly-defined spectrum occurs, which differs substantially from those found on (111) surfaces of Pt (ref.2), Rh (ref.7) or Pd (ref.8) at room temperature. These latter have been attributed to the ethylidyne, CH₃.CM₃, surface species (ref.9). For adsorption on Ni(110) there is clearly a mixture of species at room temperature.The analysis of the vibrational spectra of selected metal-cluster compounds of known structure with selected hydrocarbon ligands has helped substantially to assign the spectra of surface species in terms of bonding structures of the adsorbed species, as in the cases of the identification of (C₂H₄)M π-adsorbed (refs.5&6) and the ethylidyne CH₃.CM₃ species (ref.9). We have recently analysed the infrared and Raman spectra of the cluster compound (C₂H₂)Os₃(CO)₁₀ and its deuterium-containing analogue. The infrared frequency and intensity pattern for the A′ modes (C_S symmetry) of the two isotopomers bears a remarkable resemblance to EELS spectra previously obtained at low temperature for C₂H₂/C₂D₂ adsorbed on Pt(111) (ref.2) and (after taking into account systematic frequency shifts) for Pd(111) (ref.4). There is good evidence for believing that the structure of the hydrocarbon ligand interacting with the osmium complex takes the form

where the arrow denotes a π-bond to the third metal atom. This strongly confirms the structure for the low-temperature acetylene species on Pt(111) as proposed by Ibach and Lehwald (ref.2).Finally the room-temperature spectra for ethylene adsorbed on finely-divided silica-supported Pt and Pd catalysts have previously been interpreted in terms of the presence of MCH₂CH₂M (ref.10) and π-bonded (C₂H₄)M species (ref.11). However comparisons with the more recent EELS spectra from ethylene on Pt(111) at room temperature (ref.2) now leads to a reassignment of the 2880 cm^?1 band, on Pt, previously assigned to MCH₂CH₂M, together with a new, related,band at 1340 cm^?1 (ref.12), to the ethylidyne species CH₃CPt₃ found on the single crystal surface.More detailed analyses of the spectra reported here will be published later. Acknowledgement is given to substantial assistance for this programme of research from the Science and Engineering Research Council.     

Summary abstract: Vibrational excitations of hydrogen and oxygen on Pd(100)

EMIRS spectra for ¹²CO-¹³CO mixtures on platinum, HSO₄^? and acrylonitrile on gold and water on silver are discussed. These examples illustrate the adsorbate identification, bonding, and orientation information which EMIRS data offer to complement electrochemical Raman data and infrared reflection absorption and EELS results. The advantages of experimental fine control of the electronegativity of the metal are shown with application to studies of coupling mechanisms between adsorbed species.     

Selective desorption from the binary coadsorbate C2H6CH3FNaCl by resonant vibrational excitation with laser infrared radiation

After measuring the linear infrared absorption spectrum of the coadsorbate, selective desorption of CH₃F from the binary coadsorbate C₂H₆CH₃FNaCl under ultrahigh vacuum conditions at 12o K stimulated by resonant CO₂ laser pulses of small fluence ～ 0.1 J·cm^t?2 has been carried out. No desorption of ethane, which is slightly more volatile, but has no significant infrared absorption at the laser frequency, was observed. The primary activation step is the resonant multiphoton excitation of the most intense internal CH₃FNaCl adsorbate vibration, the CF stretching mode ν₃. The substance separation seems to indicate high localisation of the activation in this desorption and could be of interest for applications.     

Static sims studies of adsorbate structure: II. CO adsorption on Pd(111); adsorbate-adsorbate interactions on Ru(001), Ni(111) and Pd(111)

In a study of CO adsorption on Pd(111) it is shown that the secondary ion mass spectrum contains information on both adsorbate site geometry and adsorbate coverage. The fractional yields of PdCO⁺, Pd₂CO⁺ and Pd₃CO⁺, as a function of CO coverage are correlated with the changing site geometries suggested by reflection IR data. A relationship between secondary ion emission and the adsorbate-adsorbate interactions revealed by IR and EELS is also demonstrated for CO adsorption on Ru(001), Ni(111) and Pd(111).     

The adsorption and reaction of Acetonitrile on clean and oxygen covered Ag(110) surfaces

The adsorption and reaction of acetonitrile (CH₃CN) on clean and oxygen covered Ag(110) surfaces has been studied using temperature programmed reaction spectroscopy (TPRS), isotope exchange, chemical displacement reactions and high resolution electron energy loss spectroscopy (EELS). On the clean Ag(110) surface, CH₃CN was reversibly adsorbed, desorbing with an activation energy of 10 kcal mol^-1 at 166 K from a monolayer state and at 158 K from a multilayer state. Vibrational spectra of multilayer, monolayer and sub-monolayer CH₃CN were in excellent agreement with that of gas phase CH₃CN indicating that CH₃CN is only weakly bonded to the clean Ag(110) surface. On the partially oxidized surface CH₃CN reacts with atomic oxygen to form adsorbed CH₂CN, OH and H₂O in addition to forming another molecular adsorption state with a desorption peak at 240 K. This molecular state shows a CN stretching frequency of 1840 cm^-1, which is indicative of substantial rehybridization of the CN bond and is associated with side-on coordination via the π system. The CH₂CN species is stable up to 430 K, where C-H bond breaking and reformation begins, leading to the formation of CH₃CN at 480 K and HCN at 510 K and leaving only carbon on the surface. In the presence of excess oxygen atoms C-H bond breaking and reformation is more facile leading to additional desorption peaks for CH₃CN and H₂O at 420 K. This destabilizing effect of O_(a) on Ch₂CN_(a) is explained in terms of an anionic (CH₂CN^-1) species. Comparison of the vibrational spectra from CH₂CN_(a) and CD₂CN_(a) supports the following assignment for the modes of adsorbed CH₂CN: ν(Ag-C) 215: δ(CCN) 545; ϱ_t(CH₂) 695; ϱ_w(CH₂) 850; ν(C-C) 960; ϱ_r(CH₂) 1060; δ(CH₂) 1375; ν(CN) 2075; and ν(CH₂) 2940 cm^-1. These results serve to further indicate the wide applicability of the acid-base reaction concept for reactions between gas phase Brönsted acids and adsorbed oxygen atoms on solver surfaces.     

Vibrational spectra of acetylene and ethylene adsorbed on Fe(110)

Vibrational spectra of normal and deuterated acetylene and ethylene adsorbed on a Fe(110) surface have been measured by high resolution low energy electron loss spectroscopy (EELS). For both acetylene and ethylene molecular adsorption at 120 K is evident. For a proper assignment of the vibrational modes the angular profiles of most of the losses have also been measured. Application of the EELS dipole selection and the Teller-Redlich product rule favors a triangular adsorption site (μ₃ site) on Fe(110) in a trans-bent and a trans-twisted configuration for acetylene and ethylene, respectively. Furthermore, a strong distortion of the acetylene and ethylene molecules close to a sp³ hybridization state is suggested. Above 340 K acetylene starts to decompose and the formation of CH_x intermediates is indicated followed by a complete loss of hydrogen at temperatures above 540 K. Ethylene begins to decompose into acetylene and hydrogen below 300 K.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

Vanadium valency and hybridization in V-doped hafnia investigated by electron energy loss spectroscopy

The valency of vanadium, and thus indirectly the oxygen stoichiometry, of V-doped hafnia synthesized under different atmospheres have been investigated on a nanometer scale by means of electron energy loss spectroscopy (EELS). The EELS V L_2,3 spectra are compared with the results of crystal field multiplet calculations and experiments on reference vanadium oxides. The EELS spectra indicate that V-doped hafnia prepared under reducing (H₂) and neutral (Ar) atmosphere are unambiguously substituted with trivalent vanadium atoms leading to the creation of oxygen vacancies in the structure. On the contrary, stoichiometric (Hf, V)O₂ compound (i.e. V⁴⁺) is more likely to be stabilized under oxidative (air) atmospheres. We also show that the amount of hybridization alters for the different compounds studied but may in part be analyzed by high spatially resolved EELS. The crystal field multiplet calculations particularly indicate that a simple reduction of the Slater integrals gives a good account of the spectral modification induced by hybridization for the case of tetravalent vanadium atoms. Received 17 November 2000 and Received in final form 17 April 2001     

Infrared spectroscopic investigation of the adsorption of fluoromethane on sodiumchloride surfaces under ultra high vacuum

The adsorption of CH₃F on NaCl between 77 K and 250 K was investigated using infrared spectroscopy under ultra high vacuum conditions. All internal normal modes of the adsorbate were observed and assigned. Three adsorption phases were detected. The largest frequency shift with respect to the gas takes place for the most intense mode, the C-F stretch ν₃, ? 102 cm^?1 ( 10 %) for α-CH₃F-NaCl(film) on NaCl(100), while the other modes were much less influenced. No splitting of the vibrations degenerate in the gas occurs. Adsorption isotherms and the isosteric heats of adsorption were determined.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Super-hydrophobic surface on pure magnesium substrate by wet chemical method

A layer of flower-like super-hydrophobic film was fabricated on pure Mg surface by chemical etching in H₂SO₄, H₂O₂ and subsequent immersion in stearic acid (CH₃(CH₂)₁₆COOH) ethanol solution. The super-hydrophobic surface showed a static water contact angle of 154° with the sliding angle of about 3°. With scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Fourier-transform infrared (FT-IR) spectrometer, the microstructure and composition of the sample were analyzed. Results showed that the flower-like structure and the bonding of the CH₃(CH₂)₁₆COO⁻ on Mg surface can be responsible for the superior water-repellent property. Electrochemical impedance spectroscopy revealed that the transfer resistance of super-hydrophobic surface was increased about four times than bare Mg after one-hour immersion in 0.1 mol/L NaCl solution.     

Isotopic substitution shifts in methane and vibrational band assignment in the 5560-6200 cm region

The absorption spectra of the ¹²CH₄ and ¹³CH₄ molecules have been recorded and assigned in the 5560-6200 cm⁻¹ region. The effects of isotopic substitution for ¹²C by ¹³C on the methane vibrational energy levels have been calculated from an ab initio potential energy surface and compared with experiment. Comparison of the results obtained for two isotopic species allows us to confirm the vibrational assignment for the strongest bands of ¹²CH₄ in this region. Good agreement of ab initio calculations with observed energy levels has been demonstrated. A list of the assigned ¹³CH₄ lines valuable in atmospheric applications is reported.     

Reaction intermediates of methanol synthesis and the water–gas-shift reaction on the ZnO(0001) surface

The polar Zn-ZnO(0001) surface is involved in the catalysis of methanol synthesis and the water–gas-shift reaction. We use density functional theory calculations to explore the favorable binding geometries and energies of adsorption of several molecular species relevant to these reactions, namely carbon monoxide (CO), carbon dioxide (CO₂), water (H₂O) and methanol (CH₃OH). We also consider several proposed reaction intermediates, including hydroxymethyl (CH₂OH), methoxyl (CH₃), formaldehyde (CH₂O), methyl (CH₃), methylene (CH₂), formic acid (HCOOH), formate (HCOO), formyl (HCO), hydroxyl (OH), oxygen (O) and hydrogen (H). For each, we identify the preferred binding geometry at a coverage of 1/4 monolayers (ML), and report calculated vibrational frequencies that could aid in the identification of these species in experiment. We further explore the effects on the binding energy when the adsorbate coverage is lowered to 1/9 and 1/16 ML.     

The adsorption of cyclic hydrocarbons on Ru(001): II. Cyclohexane

The adsorption of cyclohexane on Ru(001) at 90 K has been investigated by thermal desorption mass spectrometry, EELS, UV photoemission and LEED. Thermal desorption indicates the adsorption of the undissociated molecule first in a chemisorbed monolayer (T_d = 200 K) with subsequent formation of multilayers (T_d = 165 K) at higher exposures. The vibrational spectrum obtained by EELS is characterized by a frequency shift of the C-H stretching mode from 2920 cm^?1 (multilayer) to 2560 cm^?1 for the chemisorbed monolayer. Off-specular EELS data indicate two different electron scattering mechanisms for the C-H stretching mode. Whereas for the C-H stretching mode of the multilayer, large angle electron impact scattering is observed, the C-H soft-mode of the monolayer is largely due to small angle dipolar scattering. The He I photoelectron spectra of cyclohexane multilayers are characteristic of the undissociated molecule. A new assignment of C(2s) and the lowest C(2p) level, based on a comparison with benzene, shows that the chemisorbed monolayer is characterized by the absence of emission or broadening of the 2a_1u level. This is attributed to C_3v symmetry of the chemisorbed layer and to a possible interaction of the 2a_Iu orbital with the metal surface.     

Electronic excitations on clean and adsorbate-covered oxide surfaces

We have studied electronic excitations at the surfaces of NiO (100), Cr₂O₃(111), and Al₂O₃(111) thin films with Electron Energy Loss Spectroscopy (EELS). On NiO (100) we observe surface electronic excitations in the energy range of the band gap which shift upon adsorption of NO. Ab initio cluster calculations show that these excitations occur within the Ni ions at the oxide surface. The (111) surface of Cr₂O₃ is characterized by distinct excitations which are also strongly influenced by the interaction with adsorbates. Temperature-dependent measurements show that two different states of the surface exist which are separated by an activation energy of about 10 meV. For Al₂O₃(111) we present data for a CO adsorbate. The oxide is quite inert with respect to CO adsorption as indicated by desorption temperatures between 38 K and 67 K. Due to the weak interaction with the substrate the a³II valence excitation of CO shows a clearly detectable vibrational splitting which has not been observed previously for a CO adsorbate in the (sub)monolayer coverage range. For several different adsorption state the lifetimes of the a³II state could be estimated from the halfwidths of the loss peaks, yielding values between 10^–15 s for the most strongly bound species and 10^–14 s for the CO multilayer.     

Surface diffusion and entrapment of simple molecules on porous silica

Interactions of simple molecules with the surface of porous silica have been investigated using time-of-flight secondary ion mass spectrometry and temperature programmed desorption. A monolayer of water diffuses into pores at temperatures higher than 110 K. Multilayers of water are also incorporated in pores via sequential surface diffusion. In contrast, a methanol monolayer tends to stay on the surface up to 150 K, and carbon dioxide diffuses into pores rather gradually. Results can be explained as the contribution of hydrogen bonds between the adsorbate–substrate and adsorbate–adsorbate interactions. The predominance of the former (latter) might be responsible for single-molecule migration of methanol and carbon-dioxide (collective diffusion of water molecules) on the surface. These molecules are entrapped at higher coordination sites in pores, as revealed from thermal desorption peaks appearing at higher temperatures than those from non-porous silica. However, no significant difference is observed in desorption kinetics of CF₂Cl₂, Kr, CH₄, and N₂ molecules between the porous and non-porous silica substrates.     

Surface properties of superparamagnetic iron oxide MR contrast agents: Ferumoxides,ferumoxtran, ferumoxsil

The surface properties of the active ingredients in AMI colloidal, superparamagnetic iron oxide magnetic resonance (MR) contrast agents are described. Scanning electron microscopy/energy dispersive X-ray elemental analyses and diffuse reflectance Fourier transform infrared spectroscopy (FTIR) spectra of ferumoxsil (AMI-121 drug substance) were consistent with the presence of a monolayer of H₂NCH₂CH₂NHCH₂CH₂CH₂Si(O⁻)₃ siloxane monomer or dimer. The X-ray photoelectron spectra (XPS) of ferumoxsil are also consistent with complete coverage of the iron oxide surface with a monolayer of siloxane. The static secondary ion mass spectra (SSIMS) of ferumoxsil showed that the siloxane film is covalently bonded (i.e., SiOFe bonds) to the iron oxide surface. The FTIR of ferumoxides (AMI-25) and Ferumoxtran (AMI-227) showed only adsorbed dextran. The XPS spectra of the dextrancoated colloids showed that Ferumoxtran has a thicker layer of dextran than ferumoxides iron oxide particles (∼5 and ∼3 nm, respectively). The SSIMS spectra of these dextran-coated colloids showed only low mass fragments due to the adsorbed dextran. The nature of the interactions of the dextran coating with the iron oxide surfaces of ferumoxides and Ferumoxtran is discussed.     

CO on Pt(111): TDS and ESD study

Electron stimulated desorption of ionic species from CO adsorbed on Pt(111) has been studied and comparison made with EELS results. The “on-top” site which, according to EELS data, fills first is observed to yield O⁺ ion. The bridge adsorption site appears to release CO⁺ during electron bombardment. Coadsorption of H₂ and CO was also examined and compared with the polycrystalline platinum case. Only very weak coadsorption effects are seen on the Pt(111) surface, as evidenced by presence of a weak low energy component associated with the O⁺ ESD energy distribution.     

Mössbauer studies of57Fe atoms isolated in CH4 and CO2 matrices

The Mössbauer absorption spectra of matrix isolated⁵⁷Fe atoms have been measured in the inert matrices CH₄ and CO₂ with matrix temperatures between ～3.3 and ～46 K. The isomer shift of the observed resonances is (?0.79±0.02) mm/s and (?0.76±0.05) mm/s with respect to iron metal at 300 K for⁵⁷Fe in CH₄ and for CO₂ respectively. This is within the experimental errors the same isomer shift as that of rare-gas matrix isolated⁵⁷Fe atoms. All spectra show quadrupole doublets due to the noncubic point symmetry of the lattice site occupied by the⁵⁷Fe atoms. The effective Debye temperatures as obtained from the temperature dependence of the resonance absorption areas are (46±4) K for the CH₄ matrix and (121±6) K for the CO₂ matrix annealed at ～20 K.