CO Stretch Bands Research Articles

High-resolution spectroscopic study of asymmetric [formula omitted] stretch [formula omitted] Torsion [formula omitted] combination band and other higher-lying vibrational fundamental, overtone, combination, and hot bands of astrophysically significant methanol [formula omitted] molecule

In this paper, the spectrum of high energy vibrational bands has been recorded in the range 1900-6000cm-1with the highest possible resolution. New assignments have been obtained for a large number of transitions belonging to several fundamental and combination bands. Varios bands of importance in the range 1950 − 3420 cm-1 are shown in Fig. 1. Notable are those belonging to a new combination band comprising the asymmetric CH3- Stretch band and OH internal rotation (or torsion) band lying in a very crowded region of the three coupled fundamental CH3- stretching bands. A large number of ΔK=±1 transitions have been observed from the ground and the first excited torsional states of the ground vibrational state. In addition, new transitions have been obtained for the torsionally excited OH- stretch band. The majority of the transitions have been confirmed using closed combination loops. In addition, detailed assignment work has been performed with improved accuracy on the overtone CO stretch band 2ν8, CO- Stretch:CH3-rock (ν8+ν7) combination band, and the overtone asymmetric CH3-bending band 2ν4. Due to an accidental state mixing in the first excited torsional state of the ground vibrational state, many forbidden transitions have been detected in the torsional band of the OH–stretch state (ν1). Lastly, a new and elegant method has been employed to obtain the pure torsional energies of many vibrational states. The most exciting finding from these studies has been the inversion of A/E energy structure. Some explanations from the literature have been reviewed, and more work is needed to understand the coupling between torsion and vibration in methanol. The work should be helpful in the astronomical search for methanol in interstellar space.

Laser-Induced Fluorescence Spectroscopy of Large Secondary Alkoxy Radicals: Part I. Spectral Overviews and Vibronic Analysis.

We report vibronically resolved laser-induced fluorescence (LIF) spectra of jet-cooled C5-C10 secondary alkoxy radicals. The LIF spectra demonstrate vibronic structures similar to smaller (C3-C4) secondary alkoxies. For 2-pentoxy and 2-hexoxy, rotationally resolved LIF spectra have also been recorded. Two types of rotational structures have been observed in vibronic bands of each molecule. Extensive quantum chemistry calculations have been performed on 2-pentoxy and 2-hexoxy. The computed results include the relative energies of conformers, their geometries, and the energy separations between the nearly degenerate à and X̃ electronic states (ΔEÃ-X̃). Based on the similarity between the vibronic structures of different secondary alkoxies and calculated molecular parameters, including the relative energies of conformers, the B̃ ← X̃ transition frequencies, and the vibrational frequencies, strong vibronic bands in the LIF spectra are assigned to the origin bands and CO stretch bands of the two lowest-energy conformers of each secondary alkoxy radical. The distinct rotational structures of the two different conformations of 2-pentoxy and 2-hexoxy will be simulated and analyzed in Part II of this series ( J. Phys. Chem. A 2021, DOI: 10.1021/acs.jpca.0c10663).

Laser-Induced Fluorescence Spectroscopy of Large Secondary Alkoxy Radicals: Part II. Rotational and Fine Structure.

Selected vibronic bands of the B̃ ← X̃ laser-induced fluorescence (LIF) spectra of jet-cooled 2-pentoxy and 2-hexoxy, including the origin and CO-stretch bands, have been measured with rotational resolution and analyzed using (1) an effective Hamiltonian that comprises a rotational part and a spin-rotation (SR) part (the "isolated-states model") and (2) a recently developed Hamiltonian in which the nearly degenerate à and X̃ states are treated together (the "coupled-states model") (see Liu, J., J. Chem. Phys. 2018, 148, 124112). The observed rotational and fine structures of the strongest vibronic bands have first been simulated using a genetic algorithm with the isolated-states model. The parameters for the simulation include rotational constants for both the X̃ and B̃ states, which can be calculated from the electronic structure theory, as well as the electronic SR constants of the X̃ state and the transition dipole moments (TDMs), both of which are predicted based on their transferability in an "orbital-fixed coordinate system" using iso-propoxy as the reference molecule. Quantum chemistry calculations suggest that the lowest two electronic (X̃ and Ã) states of secondary alkoxy radicals have small energy separations on the order of 100 cm-1 (see Part I of this series: J. Phys. Chem. A 2021, DOI: 10.1021/acs.jpca.0c10662). The electron configurations of these two nearly degenerate states have been determined by comparing the experimentally determined rotational constants and the TDMs to the ones predicted for the X̃ and à states. The experimental LIF spectra were also simulated with the coupled-states model, in which the effective spin-orbit (SO) constants (aζed) and the SO-free separation between the à and the X̃ states (ΔE0) have been determined. Molecular constants derived from fitting the rotational and fine structures of the experimental LIF spectra enabled unambiguous assignment of the observed vibronic bands to specific conformers of 2-pentoxy and 2-hexoxy as reported in Part I.

Vibrational Spectroscopic and Computational Studies on Formamide Solutions of Alkali Metal Ions

Infrared (IR) spectra were measured for formamide (FA, HCONH2) solutions of Li(ClO4) and Na(ClO4). Both CN stretch and CO stretch bands of FA are observed to undergo upshifts in the presence of the metal ions. Quantum chemical calculations were performed for Li+(FA)n (n = 1–7) and Na+(FA)n (n = 1–8) complexes in order to model the metal ions in FA solutions. In previous Raman studies of the Li+ system, the so-called chelate configuration was assumed, in which the Li+ ion was put into the center of a ring FA dimer. However, the present calculations reveal that such a configuration is in conflict with the observed band shifts. The experimental IR spectra are reproduced by adopting appropriate isomers of Li+(FA)5 and Li+(FA)6 complexes, in which all FA molecules are coordinated to Li+ via the O atom, with a configuration such that the Li+ ion and NH2 group are on the same side of the CO bond. These complexes, especially Li+(FA)6, are also successful in replicating characteristic features observed in the previous Raman spectra. Similarly, an O-bound isomer of Na+(FA)6 is consistent with the experimental IR and Raman spectra of the Na+ system. A strong coupling among the CO oscillators of FA molecules is shown to be responsible for the upshifts of the νCO modes despite the coordination via the O atom.

Laser-Induced Fluorescence and Dispersed Fluorescence Spectroscopy of Jet-Cooled Isopentoxy Radicals.

The B̃-X̃ laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled isopentoxy radicals have been obtained. The LIF spectrum of isopentoxy lacks strong transitions to the CO-stretch levels that are typical for alkoxy radicals. Instead, it contains two low-frequency vibrational progressions due to large-amplitude motions of the GG' and GG conformers involving torsion of the C1C2C3H dihedral angle. Other vibronic bands observed in the LIF spectrum are attributed to the TG conformer. Molecular carriers of the vibronic transitions in the LIF spectrum are identified by comparing the experimentally obtained spectrum and the simulated one. DF spectra of the GG and TG conformers are dominated by strong vibrational progressions of the CO-stretch mode when the origin or the CO-stretch band is pumped. When non-CO-stretch bands are pumped, the DF spectra are dominated by combination bands of the CO stretch and the pumped mode. Ã-X̃ separations of the GG and TG conformers were also determined from the DF spectra.

Infrared spectroscopic and computational studies on formamide solutions of Ca2+. Vibrational frequencies of formamide and modes of coordination to Ca2+

Infrared spectroscopy for formamide (FA) solutions of Ca(ClO4)2 shows that both CN stretch (νCN) and CO stretch (νCO) bands of FA undergo upshifts in the presence of Ca2+. Modeling of Ca2+ in FA solutions is accomplished by quantum chemical calculations for Ca2+(FA)n (n = 1–8) complexes with Polarizable Continuum Model (PCM). The calculations indicate that bidentate Ca2+(FA)4 complexes are not consistent with the observed upshift of the νCN band, although a bidentate coordination of four FA molecules via both O and N atoms was assumed in a previous study of the same system. The experimental results are reasonably reproduced by adopting Ca2+(FA)7 and Ca2+(FA)8 complexes with a monodentate coordination of all FA molecules via the O atom. A strong coupling among the CO oscillators is shown to be responsible for the upshifts of the νCO modes despite the O atom coordination.

Quantum chemical studies of redox properties and conformational changes of a four-center iron CO2 reduction electrocatalyst.

The CO2 reduction electrocatalyst [Fe4N(CO)12]- (abbrev. 1-) reduces CO2 to HCO2- in a two-electron, one-proton catalytic cycle. Here, we employ ab initio calculations to estimate the first two redox potentials of 1- and explore the pathway of a side reaction involving CO dissociation from 13-. Using the BP86 density functional approximation, the redox potentials were computed with a root mean squared error of 0.15 V with respect to experimental data. High temperature Born-Oppenheimer molecular dynamics was employed to discover a reaction pathway of CO dissociation from 13- with a reaction energy of +10.6 kcal mol-1 and an activation energy of 18.8 kcal mol-1; including harmonic free energy terms, this yields ΔGsep = 1.4 kcal mol-1 for fully separated species and ΔG‡ = +17.4 kcal mol-1, indicating CO dissociation is energetically accessible at ambient conditions. The analogous dissociation pathway from 12- has a reaction energy of 22.1 kcal mol-1 and an activation energy of 22.4 kcal mol-1 (ΔGsep = 12.8 kcal mol-1, ΔG‡ = +18.1 kcal mol-1). Our computed harmonic vibrational analysis of [Fe4N(CO)11]3- or 23- reveals a distinct CO-stretching peak red-shifted from the main CO-stretching band, pointing to a possible vibrational signature of dissociation. Multi-reference CASSCF calculations are used to check the assumptions of the density functional approximations that were used to obtain the majority of the results.

Dispersed Fluorescence Spectroscopy of Jet-Cooled 2-, 3-, and 4-Methylcyclohexoxy Radicals.

Vibrational structures of the nearly degenerate X̃ and à states of the 2-, 3-, and 4-methylcyclohexoxy (MCHO) radicals were studied by jet-cooled dispersed fluorescence (DF) spectroscopy. The observed transitions were assigned on the basis of vibrational frequencies and Franck-Condon factors predicted by quantum chemical calculations. Intensities of vibronic transitions in the DF spectra are dependent on the laser-induced fluorescence (LIF) bands pumped in the experiment, which can be explained by the difference in geometry and symmetry between the lower X̃/à states and the highly excited B̃ state. All three studied isomers of MCHO have close-lying X̃ and à states although their energy separations are affected by the position of the methyl group. It is suggested by quantum chemical calculations that the lowest-energy conformers of all three isomers have the half-filled orbital oriented perpendicular to the OCH plane, which is consistent with the observed relative intensities of the B̃ → X̃ and B̃ → à origin bands. When the origin and the CO-stretch bands of the B̃ ← X̃ LIF excitation spectra were pumped, the DF spectra were dominated by CO-stretch progressions. When non-CO-stretch vibrational levels of the B̃ state were pumped, progressions of CO-stretch modes combined with the pumped vibrational mode were observed. Excited-state vibrational population relaxation from the CO stretch level to the vibrational ground level and from combination levels of the CO stretch mode and other vibrational modes to the non-CO stretch modes was observed. Analysis of the DF spectra confirms the previous conclusion that all strong LIF bands observed under jet-cooled conditions belong to a single conformer of each positional isomer (Lin et al. RSC Adv. 2012, 2, 583-589).

Ultrafast dynamics in iron tetracarbonyl olefin complexes investigated with two-dimensional vibrational spectroscopy

The dynamics of iron tetracarbonyl olefin complexes has been investigated using two-dimensional infrared (2D-IR) spectroscopy. Cross peaks between all CO-stretching bands show that the CO-stretch modes are coupled, and from the cross-peak anisotropies we can confirm previous assignments of the absorption bands. From the pump-probe delay dependence of the diagonal peaks in the 2D-IR spectrum we obtain a correlation time of ∼3 ps for the spectral fluctuations of the CO-stretch modes. We observe a multi-exponential pump-probe delay dependence of the cross-peak intensities, with rate constants ranging from 0.1 ps(-1) to 0.6 ps(-1). To determine whether this delay dependence originates from fluxionality of the complex or from intramolecular vibrational relaxation (IVR), we modulate the free-energy barrier of fluxional rearrangement by varying the pi-backbonding capacities of the olefin ligand in two iron tetracarbonyl olefin complexes: Fe(CO)(4)(cinnamic acid) and Fe(CO)(4)(dimethyl fumarate). Since the pi-backbonding strongly influences the rate of fluxionality, comparing the dynamics in the two complexes allows us to determine to what extent the observed dynamics is caused by fluxionality. We conclude that on the time scale of our experiments (up to 100 ps) the cross-peak dynamics in the iron complexes is determined by intramolecular vibrational energy relaxation. Hence, in contrast to previously investigated irontricarbonyl and ironpentacarbonyl complexes, iron tetracarbonyl olefin complexes exhibit no fluxionality on the picosecond time scale.

Quantum Cascade Laser Spectroscopy and Photoinduced Chemistry of Al–(CO)n Clusters in Helium Nanodroplets

Helium nanodroplet isolation and a tunable quantum cascade laser are used to probe the fundamental CO stretch bands of aluminum carbonyl complexes, Al-(CO)(n) (n ≤ 5). The droplets are doped with single aluminum atoms via the resistive heating of an aluminum wetted tantalum wire. The downstream sequential pick-up of CO molecules leads to the rapid formation and cooling of Al-(CO)(n) clusters within the droplets. Near 1900 cm(-1), rotational fine structure is resolved in bands that are assigned to the CO stretch of a linear (2)Π(1/2) Al-CO species and the asymmetric and symmetric CO stretch vibrations of a planar C(2v) Al-(CO)(2) complex in a (2)B(1) electronic state. Bands corresponding to clusters with n ≥ 3 lack resolved rotational fine structure; nevertheless, the small frequency shifts from the n = 2 bands indicate that these clusters consist of an Al-(CO)(2) core with additional CO molecules attached via van der Waals interactions. A second n = 2 band is observed near the CO stretch of Al-CO, indicating a local minimum on the n = 2 potential consisting of an "unreacted" (Al-CO)-CO cluster. The line width of this band is ∼0.3 cm(-1), which is about 30 times broader than the transitions within the Al-CO band. The additional broadening is consistent with a homogeneous mechanism corresponding to a rapid vibrational excitation induced reaction within the (Al-CO)-CO cluster to form the covalently bonded Al-(CO)(2) complex. Ab initio CCSD(T) calculations and natural bond orbital (NBO) analyses are carried out to investigate the nature of the bonding in the n = 1, 2 complexes. The NBO calculations show that both π-donation (from the occupied aluminum p orbital into a π* antibonding CO orbital) and σ-donation (from CO into the empty aluminum p orbitals) play a significant role in the bonding, analogous to transition-metal carbonyl complexes. The large red shift observed for the CO stretch vibrations is consistent with this bonding analysis.

Fourier transform synchrotron spectroscopy of torsional and CO-stretching bands of CH 317OH

The Fourier transform spectrum of the CH 3 17OH isotopologue of methanol has been recorded in the 65–1200 cm −1 spectral region at a resolution of 0.00096 cm −1 using synchrotron source radiation at the Canadian Light Source. Here we present an extension to higher torsional states of our investigation of the torsion–rotation transitions within the small-amplitude vibrational ground state, now including assignments of more than 16 500 lines involving quantum numbers in the ranges v t ⩽ 3, J ⩽ 30 and | K| ⩽ 12, as well as a study of the strong CO-stretching band centered at 1020 cm −1. Energy term values have been determined for assigned ground and CO-stretching levels by use of the Ritz program, and have been fitted to series expansions in powers of J( J + 1) to determine substate origins and effective B values. Several Fermi anharmonic and Coriolis level-crossing resonances coupling the CO stretch with high torsional ground-state levels have been identified and characterized. The study is motivated by astrophysical applications, with a principal aim being the compilation of an extensive set of energy term values to permit prediction of astronomically observable sub-millimetre transitions to within an uncertainty of a few MHz.

Fourier transform spectroscopy of the CO-stretching band of O-18 methanol

The high-resolution Fourier transform spectrum of the ν 8 CO-stretching band of CH 3 18OH between 900 and 1100 cm −1 has been recorded at the Canadian Light Source (CLS) synchrotron facility in Saskatoon, and the majority of the torsion–rotation structure has been analyzed. For the ν t = 0 torsional ground state, subbands have been identified for K values from 0 to 11 for A and E torsional symmetries up to J values typically well over 30. For ν t = 1, A and E subbands have been assigned up to K = 7, and several ν t = 2 subbands have also been identified. Upper-state term values determined from the assigned transitions using the Ritz program have been fitted to J( J + 1) power-series expansions to obtain substate origins and sets of state-specific parameters giving a compact representation of the substate J-dependence. The ν t = 0 subband origins have been fitted to effective molecular constants for the excited CO-stretching state and a torsional barrier of 377.49(32) cm −1 is found, representing a 0.89% increase over the ground-state value. The vibrational energy for the CO-stretch state was found to be 1007.49(7) cm −1. A number of subband-wide and J-localized perturbations have been seen in the spectrum, arising both from anharmonic and Coriolis interactions, and several of the interacting states have been identified.

New assignments, line intensities, and HITRAN database for CH 3OH at 10 μm

The Fourier transform spectrum of CH 3OH in the 10 μm region has been re-examined at higher pressure and path length than heretofore, as part of a program to provide comprehensive CH 3OH spectral data for astrophysical and atmospheric applications. With the increase in spectral sensitivity, it has been possible to assign new torsionally excited ν 12=1 and ν 12=2 subbands plus further high- K, ν 12=0 subbands of the ν 8 CO-stretching band. Upper-state term values have been determined, and have been fitted to J( J+1) power-series expansions in order to obtain the excited ν 8 substate origins. A variety of weaker subbands from other modes has also been identified in the 10 μm spectrum including ν 12=0, ν 12=1, and ν 12=0←1 torsional subbands of the ν 7 in-plane CH 3 rock, ν 12=0←1 and ν 12=0←2 torsional combination subbands of the ν 6 OH bend, and ν 12=0←2 subbands of the ν 5 symmetric CH 3 bend. Line intensities have been retrieved line-by-line from the spectra. A large set of “unperturbed” ν 8 transitions has been modeled using the same type of multi-parameter effective Hamiltonian employed successfully for the ground state, with inclusion of the intensities of a subset of the stronger ν 8 spectral lines in the fitting in order to obtain appropriate transition dipole terms. Together, a 10 μm methanol database in HITRAN format has been generated.

Ultrafast Chelation Dynamics of Cyclopentadienyl Manganese Tricarbonyl Derivatives with Pendant Sulfides

The photoinduced dynamics of two new [η5-C5H4C(O)R]Mn(CO)3 complexes 2 (R = CH(SCH3)2) and 3 (R = C(SCH3)3) have been investigated in n-heptane solution on the ps to μs time scale by UV-pump IR-probe transient absorption spectroscopy. Irradiation of 2 at 266 or 289 nm induces CO loss to yield two initial products in approximately equal abundance, assigned by their CO-stretching bands to be a heptane solvate of the unsaturated Mn fragment and a ring-formed product in which the pendant sulfide moiety is coordinated to the metal center. In direct analogy with the previously observed behavior of [η5-C5H4C(O)CH2(SCH3)]Mn(CO)3 (1), the solvate reacts through a secondary pathway to afford the S-bound product within 200 ns. Irradiation of 3 under identical conditions yields the chelated product exclusively, with no evidence of a competing solvation pathway.

Infrared Spectroscopy of Aqueous Carboxylic Acids: Malic Acid

Quantitative infrared (IR) titration of 1.80 M malic acid is presented where factor analysis (FA) was used to obtain the principal species' spectra and their abundances. Three malic species and three water species were obtained. The distribution of the species as a function of pH was made from which their pKa values were determined. The experimental points of the distribution curves correspond to the values calculated from the thermodynamic equilibrium equations. A precise determination of aqueous malic IR bands was obtained from the real spectra of the malic species. The hydrates' hydration numbers were determined to be 2.0 ± 1.0, 3.0 ± 2.0, and 4.0 ± 0.5 for malic acid, mono-, and disodium malate, respectively. The hydrates are stable throughout the pH range where the species are present. The double and single CO stretch bands of malic acid are situated at 1719 and 1272 cm-1, respectively. The antisymmetric and symmetric CO stretch bands of mono- and disodium malate are situated at 1580, 1400 cm-1 and 1563, 1395 cm-1, respectively. Malic acid shows four very broad bands in the 3800−1800 cm-1 region as a continuous absorption assigned to the OH stretch of hydrogen bonded water and alcoholic groups to carboxylic groups. The 2930 and 2580 cm-1 bands, which are far from the 3500 cm-1 band, indicate strong hydrogen bonds. Disodium malate shows one large band at 3320 cm-1 assigned to the OH stretch of solvated water and alcoholic groups. Monosodium malate has the bands of both malic and disodium malate slightly displaced, but with half their intensities.

Structural Dynamics of Myoglobin: LIGAND MIGRATION AMONG PROTEIN CAVITIES STUDIED BY FOURIER TRANSFORM INFRARED/TEMPERATURE DERIVATIVE SPECTROSCOPY

Fourier transform infrared (FTIR) spectroscopy in the CO stretch bands combined with temperature derivative spectroscopy (TDS) was used to characterize intermediate states obtained by photolysis of two sperm whale mutant myoglobins, YQR (L29(B10)Y, H64(E7)Q, T67(E10)R) and YQRF (with an additional I107(G8)F replacement). Both mutants assume two different bound-state conformations, A(0) and A(3), which can be distinguished by their different CO bands near 1965 and 1933 cm(-1). They most likely originate from different conformations of the Gln-64 side chain. Within each A substate, a number of photoproduct states have been characterized on the basis of the temperature dependence of recombination in TDS experiments. Different locations and orientations of the ligand within the protein can be distinguished by the infrared spectra of the photolyzed CO. Recombination from the primary docking site, B, near the heme dominates below 50 K. Above 60 K, ligand rebinding occurs predominantly from a secondary docking site, C', in which the CO is trapped in the Xe4 cavity on the distal side, as shown by crystallography of photolyzed YQR and L29W myoglobin CO. Another kinetic state (C") has been identified from which rebinding occurs around 130 K. Moreover, a population appearing above the solvent glass transition at approximately 180 K (D state) is assigned to rebinding from the Xe1 cavity, as suggested by the photoproduct structure of the L29W sperm whale myoglobin mutant. For both the YQR and YQRF mutants, rebinding from the B sites near the heme differs for the two A substates, supporting the view that the return of the ligand from the C', C", and D states is not governed by the recombination barrier at the heme iron but rather by migration to the active site. Comparison of YQR and YQRF shows that access to the Xe4 site (C') is severely restricted by introduction of the bulky Phe side chain at position 107.

FT-Infrared spectroscopic studies of the iron ligand CO stretch mode of iNOS oxygenase domain: effect of arginine and tetrahydrobiopterin.

The iron ligand CO stretch vibration mode of the inducible nitric oxide synthase oxygenase domain (iNOSox) has been studied from 20 to 298 K. iNOSox in the absence of arginine reveals a temperature-dependent equilibrium of two major conformational substates with CO stretch bands centered at about 1945 and 1954 cm(-)(1). This behavior is not qualitatively changed when tetrahydrobiopterin (H(4)B) is bound. Arginine binding changes significantly the spectrum by formation of a sharp CO stretch mode band at about 1905 cm(-)(1) and indicates the formation of a hydrogen bond to the CO ligand. For temperatures lower than 250 K, the stretch vibration frequency decreases almost linearly with decreasing temperature and indicates that the coupling between the CO ligand and the arginine/protein in the active site via the hydrogen bond is very strong. Flashphotolysis of the CO ligand carried out at 25 K revealed the CO stretch mode of the photodissociated CO ligand trapped in the heme pocket. There is a negative linear relation between the stretch vibration frequencies of the photodissociated and the iron-bound CO indicating that the photodissociated ligand stays near the heme.

Fourier Transform Spectrum and Term Values for the CO-Stretching Mode of CD3OH Methanol

The Fourier transform infrared (FTIR) spectrum of the CO-stretching fundamental band of CD3OH has been recorded at a resolution of 0.002 cm-1. Assignments are reported for 35 subbands in the n = 0 ground torsional state, covering K = 0 to 9 for all torsional symmetries plus K = 10 A, and 12 assorted A and E subbands in the n = 1 first excited torsional state ranging from K = 0 up to K = 5. The subband wavenumbers have been fitted to J(J + 1) power-series energy expansions to obtain subband origins and a compact representation of the spectral observations. With the use of known ground-state energies, CO-stretch energy term values have been determined and tabulated. Least-squares fitting of the subband origins to a fourth-order Hamiltonian model for the CO-stretch mode is discussed.

Sensitivity of Compressed Carbon Monoxide Adlayers on Platinum(111) Electrodes to Long-Range Substrate Structure: Influence of Monoatomic Steps

Infrared spectra are reported for saturated CO adlayers on highly ordered Pt(111) and related stepped surfaces in aqueous 0.1 M HClO4 with the objective of ascertaining the importance of long-range substrate structure to the surface-binding configurations of the compressed adlayers. On Pt(111) in the presence of CO in solution, a pair of CO-stretching (νCO) bands are obtained throughout the accessible potential region below the onset of adsorbate electrooxidation that are diagnostic of atop/3-fold hollow coordination, fingerprinting the (2 × 2)-3CO (θCO = 0.75) compressed adlayer also characterized earlier by scanning tunneling microscopy (STM). This finding differs from some earlier reports, which indicate a structural conversion to an atop/bridging CO binding arrangement at higher potentials: this transition was seen to be triggered here only by the onset of adsorbate electrooxidation. The corresponding spectral fingerprint obtained in the absence of CO in solution (i.e., for the irreversibly adsorbed case) indicates a mixture of 3-fold and 2-fold bridging along with atop CO, suggesting the presence of less compressed adlayer domains, consistent with the known lower packing densities (θCO ≈ 0.65 to 0.7). The introduction of even occasional (110) or (100) steps, specifically for Pt(17,17,15) and -(17,15,15) (i.e, n(111) × (110) and n(111) × (100) where n = 16], yields significantly different νCO spectra, especially for the irreversibly adsorbed case which indicate the predominant presence of bridging rather than 3-fold hollow CO, most clearly at higher potentials. The presence of higher (110) step densities attenuates as well as broadens further the multifold νCO bands, eventually (for n = 2) yielding a spectral fingerprint closely akin to that of Pt(110) itself. Increasing the (100) step density (to n = 5,2) also removes the multifold νCO features associated with the (111) terraces, bridging νCO bands indicative of bonding on the (100) step sites becoming prevalent. The importance of long-range substrate order in determining the compressed CO adlayer arrangements on Pt(111) terraces is assessed in the light of these findings.

Structural heterogeneity and ligand binding in carbonmonoxy myoglobin crystals at cryogenic temperatures.

We have characterized the ligand-rebinding behavior of single crystal native sperm whale carbonmonoxy myoglobin (swMbCO) (space group P21) and a synthetic mutant swMbCO (space group P6) at cryogenic temperatures by using temperature-derivative spectroscopy (TDS) with monitoring of the CO stretch bands in the mid-infrared. Crystals were studied at pH 5.1 and 7.0 for native swMbCO and at pH 7.0 for the mutant; both short-flash and extended illumination protocols were performed. The TDS analysis yields the enthalpy barrier distributions for recombination in the individual taxonomic (A) substates, A0, A1, and A3. A single gaussian barrier distribution gave a good first-order description but was insufficient to precisely fit the data within each substate. An additional minority species was necessary to model the enhanced rebinding below 30 K, which likely appears because of quantum tunneling. The peak positions and widths of the enthalpy distributions are similar for the P21 and P6 crystal forms, indicating that crystal-packing forces have only very minor effects on the structure at the active site. Moreover, the widths of the (dominant) distributions are qualitatively similar to those observed with glycerol-water solutions, which shows that the degree of structural heterogeneity is similar for solution and crystalline samples. For the A3 substate, a significantly lower peak enthalpy was obtained (by approximately 4 kJ/mol) than for solutions, while the peak shifts in the A0 and A1 substates were small. In samples cooled under illumination, discrete populations with higher rebinding barriers were observed. Concomitant changes in the stretch absorption of the photodissociated CO (B states) only occur between 100 and 130 K. They likely arise from movements of the ligand in the heme pocket between discrete sites.