IR Photodissociation Spectroscopy Research Articles

Structural Investigation of Small Nickel-Ethanol Clusters Using Vibrational Spectroscopy in a Molecular Beam.

The structural identification of small nickel clusters with ethanol can help to understand fundamental steps for heterogenous catalysis. We investigate the rows [Nix (EtOH)1 ]+ with x=1-4, and [Ni2 (EtOH)y ]+ with y=1-3 via IR photodissociation spectroscopy in a molecular beam experiment. Analyzing the CH- and OH-stretching frequencies and comparing these experimental results with density functional theory (DFT) calculations on the PW91/6-311+G(d,p) level leads to the identification of intact motifs for all clusters and hints for C-O cleavage of the ethanol in two particular cases. Furthermore, we analyze the effects of frequency shifts with the increasing clusters sizes using the results of natural bond orbitals (NBO) analyses and an energy decomposition method.

Do Stereochemical Effects Overcome a Charge-Induced Perturbation in Isolated Protonated Cyclo(Tyr-Tyr)?

Two diastereomers of the protonated diketopiperazine (DKP) dipeptide cyclo(Tyr-Tyr), namely, cyclo(LTyr-LTyr)H+ and cyclo(LTyr-DTyr)H+, are studied in a cryogenic ion trap by means of IR photodissociation spectroscopy combined with quantum chemical calculations. The two diastereomers have similar structures in which one of the rings is folded over the DKP ring and the other one is extended in a trans geometry, allowing a strong OH+···π interaction to take place. This contrasts to the observation of a stacked geometry for neutral cyclo(LTyr-LTyr) only under supersonic expansion conditions that do not exist for cyclo(LTyr-DTyr). In the protonated form, the strength of the OH+···π interaction is different for the two diastereomers, resulting in a ∼110 cm-1 difference in the ν(OH+) frequency and a smaller but clearly identifiable difference in the protonated amide ν(NH) frequency. Stereochemical effects are therefore still evidenced despite the strong perturbation due to the excess charge.

Structures and Chemical Rearrangements of Benzoate Derivatives Following Gas Phase Decarboxylation.

Decarboxylation of carboxylate ions in the gas phase provides a useful window into the chemistry displayed by these reactive carbanion intermediates. Here, we explore the species generated by decarboxylation of two benzoate derivatives: 2-formylbenzoate (2FBA) and 2-benzoylbenzoate (2BBA). The nascent product anions are transferred to a cryogenic ion trap where they are cooled to ∼15 K and analyzed by their pattern of vibrational bands obtained with IR photodissociation spectroscopy of weakly bound H2 molecules. The structures of the quenched species are then determined by comparison of these spectra with those predicted by electronic structure calculations for local minima on the potential energy surface. The 2-phenide carbanion generated by decarboxylation of 2FBA occurs in two isomeric forms that differ in the orientation of the formyl group, both of which yield a very large (∼110 cm-1) redshift in the stretching frequency of the H2 molecule attached to the anionic carbon center. Although calculated to be a local minimum, the analogous 2-phenide species could not be isolated upon decarboxylation of 2BBA. Rather, the anionic product adopts a ring-closed structure, indicating efficient nucleophilic attack on the pendant phenyl group by the nascent phenide. The barrier for ring closing is evaluated with electronic structure calculations.

Multianalytical Approach for Deciphering the Specific MS/MS Transition and Overcoming the Challenge of the Separation of a Transient Intermediate, Quinonoid Dihydrobiopterin.

Despite recent technological developments in analytical chemistry, separation and direct characterization of transient intermediates remain an analytical challenge. Among these, separation and direct characterization of quinonoid dihydrobiopterin (qH2Bip), a transient intermediate of tetrahydrobiopterin (H4Bip)-dependent hydroxylation reactions, essential in living organisms, with important and varied human pathophysiological impacts, are a clear illustration. H4Bip regeneration may be impaired by competitive nonenzymatic autoxidation reactions, such as isomerization of qH2Bip into a more stable 7,8-H2Bip (H2Bip) isomer, and subsequent nonenzymatic oxidation reactions. The quinonoid qH2Bip intermediate thus plays a key role in H4Bip-dependent hydroxylation reactions. However, only a few experimental results have indirectly confirmed this finding while revealing the difficulty of isolating qH2Bip from H4Bip-containing solutions. As a result, no current H4Bip assay method allows this isomer to be quantified even by liquid chromatography-tandem mass spectrometry (MS/MS). Here, we report isolation, structural characterization, and abundance of qH2Bip formed upon H4Bip autoxidation using three methods integrated into MS/MS. First, we characterized the structure of the two observed H2B isomers using IR photodissociation spectroscopy in conjunction with quantum chemical calculations. Then, we used differential ion mobility spectrometry to fully separate all oxidized forms of H4Bip including qH2Bip. These data are consistent and show that qH2Bip can also be unambiguously identified thanks to its specific MS/MS transition. This finding paves the way for the quantification of qH2Bip with MS/MS methods. Most importantly, the half-life value of this intermediate is nearly equivalent to that of H4Bip (tens of minutes), suggesting that an accurate method of H4Bip analysis should include the quantification of qH2Bip.

Real-time observation of photoionization-induced water migration dynamics in 4-methylformanilide-water by picosecond time-resolved infrared spectroscopy and ab initio molecular dynamics simulations.

A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the trans-4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics. Time constants for the initial to the intermediate and hot product and to the final product are obtained. The acceleration of the dynamics by methyl substitution and the strong contribution of intracluster vibrational energy redistribution in the termination of the solvation dynamics is suggested. This picture is well confirmed by the ab initio on-the-fly molecular dynamics simulations. Vibrational assignments of 4MetFA and 4MetFA-W in the neutral (S0 and S1) and ionic (D0) electronic states measured by ns IR dip and electron-impact IR photodissociation spectroscopy are also discussed prior to the results of time-resolved spectroscopy.

Characterization of the non-covalent docking motif in the isolated reactant complex of a double proton-coupled electron transfer reaction with cryogenic ion spectroscopy.

The solution kinetics of a proton-coupled electron transfer reaction involving two-electron oxidation of a Ru compound with concomitant transfer of two protons to a quinone derivative have been interpreted to indicate the formation of a long-lived intermediate between the reactants. We characterize the ionic reactants, products, and an entrance channel reaction complex in the gas phase using high-resolution mass spectrometry augmented by cryogenic ion IR photodissociation spectroscopy. Collisional activation of this trapped entrance channel complex does not drive the reaction to products but rather yields dissociation back to reactants. Electronic structure calculations indicate that there are four low-lying isomeric forms of the non-covalently bound complex. Comparison of their predicted vibrational spectra with the observed band pattern indicates that the C=O groups of the ortho-quinone attach to protons on two different -NH2 groups of the reactant scaffold, exhibiting strong O-H-N contact motifs. Since collisional activation does not lead to the products observed in the liquid phase, these results indicate that the reaction most likely proceeds through reorientation of the H-atom donor ligand about the metal center.

Photodissociation Spectroscopy of Cold Protonated Synephrine: Surprising Differences between IR-UV Hole-Burning and IR Photodissociation Spectroscopy of the O-H and N-H Modes.

We report the UV and IR photofragmentation spectroscopies of protonated synephrine in a cryogenically cooled Paul trap. Single (UV or IR) and double (UV-UV and IR-UV) resonance spectroscopies have been performed and compared to quantum chemistry calculations, allowing the assignment of the lowest-energy conformer with two rotamers depending on the orientation of the phenol hydroxyl (OH) group. The IR-UV hole burning spectrum exhibits the four expected vibrational modes in the 3 μm region, i.e., the phenol OH, Cβ-OH, and two NH2+ stretches. The striking difference is that, among these modes, only the free phenol OH mode is active through IRPD. The protonated amino group acts as a proton donor in the internal hydrogen bond and displays large frequency shifts upon isomerization expected during the multiphoton absorption process, leading to the so-called IRMPD transparency. More interestingly, while the Cβ-OH is a proton acceptor group with moderate frequency shift for the different conformations, this mode is still inactive through IRPD.

Triple Bonds Between Iron and Heavier Group 15 Elements in AFe(CO)3− (A=As, Sb, Bi) Complexes

AbstractHeteronuclear transition‐metal–main‐group‐element carbonyl complexes of AsFe(CO)3−, SbFe(CO)3−, and BiFe(CO)3− were produced by a laser vaporization supersonic ion source in the gas phase, and were studied by mass‐selected IR photodissociation spectroscopy and advanced quantum chemistry methods. These complexes have C3v structures with all of the carbonyl ligands bonded on the iron center, and feature covalent triple bonds between bare Group 15 elements and Fe(CO)3−. Chemical bonding analyses on the whole series of AFe(CO)3− (A=N, P, As, Sb, Bi, Mc) complexes indicate that the valence orbitals involved in the triple bonds are hybridized 3d and 4p atomic orbitals of iron, leading to an unusual (dp–p) type of transition‐metal–main‐group‐element multiple bonding. The σ‐type three‐orbital interaction between Fe 3d/4p and Group 15 np valence orbitals plays an important role in the bonding and stability of the heavier AFe(CO)3− (A=As, Sb, Bi) complexes.

Triple Bonds Between Iron and Heavier Group 15 Elements in AFe(CO)3- (A=As, Sb, Bi) Complexes.

Heteronuclear transition-metal-main-group-element carbonyl complexes of AsFe(CO)3- , SbFe(CO)3- , and BiFe(CO)3- were produced by a laser vaporization supersonic ion source in the gas phase, and were studied by mass-selected IR photodissociation spectroscopy and advanced quantum chemistry methods. These complexes have C3v structures with all of the carbonyl ligands bonded on the iron center, and feature covalent triple bonds between bare Group 15 elements and Fe(CO)3- . Chemical bonding analyses on the whole series of AFe(CO)3- (A=N, P, As, Sb, Bi, Mc) complexes indicate that the valence orbitals involved in the triple bonds are hybridized 3d and 4p atomic orbitals of iron, leading to an unusual (dp-p) type of transition-metal-main-group-element multiple bonding. The σ-type three-orbital interaction between Fe 3d/4p and Group 15 np valence orbitals plays an important role in the bonding and stability of the heavier AFe(CO)3- (A=As, Sb, Bi) complexes.

The Structure of Diphenyl Ether-Methanol in the Electronically Excited and Ionic Ground States: A Combined IR/UV Spectroscopic and Theoretical Study.

Diphenyl ether offers competing docking sites for methanol: the ether oxygen acts as a common hydrogen-bond acceptor and the π system of each phenyl ring allows for OH-π interactions driven by electrostatic, induction, and dispersion forces. Based on investigations in the electronic ground state (S0 ), we present a detailed study of the electronically excited state (S1 ) and the ionic ground state (D0 ), in which an impact on the structural preference is expected compared with the S0 state. Dispersion forces in the electronically excited state were analyzed by comparing the computed binding energies at the coupled-cluster-singles (CCS) and approximate coupled-cluster-singles-doubles levels of theory (CC2 approximation). By applying UV/IR/UV spectroscopy, we found a more strongly bound OH-π structure in the S1 state compared with the S0 state, in agreement with spin-component-scaled CC2 calculations. A structural rearrangement into a non-hydrogen-bonded structure takes places upon ionization in the D0 state, which was revealed by using IR photodissociation spectroscopy and confirmed by theory.

Effects of Charge Transfer on the Adsorption of CO on Small Molybdenum-Doped Platinum Clusters.

The interaction of carbon monoxide with platinum alloy nanoparticles is an important problem in the context of fuel cell catalysis. In this work, molybdenum-doped platinum clusters have been studied in the gas phase to obtain a better understanding of the fundamental nature of the Pt-CO interaction in the presence of a dopant atom. For this purpose, Ptn+ and MoPtn-1+ (n=3-7) clusters were studied by combined mass spectrometry and density functional theory calculations, making it possible to investigate the effects of molybdenum doping on the reactivity of platinum clusters with CO. In addition, IR photodissociation spectroscopy was used to measure the stretching frequency of CO molecules adsorbed on Ptn+ and MoPtn-1+ (n=3-14), allowing an investigation of dopant-induced charge redistribution within the clusters. This electronic charge transfer is correlated with the observed changes in reactivity.

Solvent-Driven Reductive Activation of CO2 by Bismuth: Switching from Metalloformate Complexes to Oxalate Products.

In this work, we investigated how the reductive activation of CO2 with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass-selected [Bi(CO2 )n ]- cluster ions was used to follow the structural evolution of the core ion with increasing cluster size. We interpreted the IR spectra by comparison with density-functional-theory calculations. The results show that CO2 binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO- . Solvation with additional CO2 molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.

ChemInform Abstract: Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides.

AbstractThe complex (μ2‐O2)PrO2 and the linear core‐containing PrO2+ complexes are observed both in the gas phase by laser vaporization of Pr in He2 seeded with a pulsed 30—40% O2 stream (1‐1.2 MPa) and in solid Ar matrices analyzed by matrix isolation IR and IR photodissociation spectroscopy (0.2—0.5 mJ/pulse, 850—1600 cm‐1) with TOF‐MS‐selected [(PrO2)+(O2)n] cations.

IR photodissociation spectroscopy of (OCS)n(+) and (OCS)n(-) cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions.

Infrared photodissociation (IRPD) spectra of (OCS)n(+) and (OCS)n(-) (n = 2-6) cluster ions are measured in the 1000-2300 cm(-1) region; these clusters show strong CO stretching vibrations in this region. For (OCS)2 +) and (OCS)2(-), we utilize the messenger technique by attaching an Ar atom to measure their IR spectra. The IRPD spectrum of (OCS)2 (+)Ar shows two bands at 2095 and 2120 cm(-1). On the basis of quantum chemical calculations, these bands are assigned to a C2 isomer of (OCS)2 (+), in which an intermolecular semi-covalent bond is formed between the sulfur ends of the two OCS components by the charge resonance interaction, and the positive charge is delocalized over the dimer. The (OCS)n(+) (n = 3-6) cluster ions show a few bands assignable to "solvent" OCS molecules in the 2000-2080 cm(-1) region, in addition to the bands due to the (OCS)2(+) ion core at ∼2090 and ∼2120 cm(-1), suggesting that the dimer ion core is kept in (OCS)3-6(+). For the (OCS)n(-) cluster anions, the IRPD spectra indicate the coexistence of a few isomers with an OCS(-) or (OCS)2(-) anion core over the cluster range of n = 2-6. The (OCS)2(-)Ar anion displays two strong bands at 1674 and 1994 cm(-1). These bands can be assigned to a Cs isomer with an OCS(-) anion core. For the n = 2-4 anions, this OCS(-) anion core form is dominant. In addition to the bands of the OCS(-) core isomer, we found another band at ∼1740 cm(-1), which can be assigned to isomers having an (OCS)2(-) ion core; this dimer core has C2 symmetry and (2)A electronic state. The IRPD spectra of the n = 3-6 anions show two IR bands at ∼1660 and ∼2020 cm(-1). The intensity of the latter component relative to that of the former one becomes stronger and stronger with increasing the size from n = 2 to 4, which corresponds to the increase of "solvent" OCS molecules attached to the OCS(-) ion core, but it suddenly decreases at n = 5 and 6. These IR spectral features of the n = 5 and 6 anions are ascribed to the formation of another (OCS)2(-) ion core having C2v symmetry with (2)B2 electronic state.

Structure and Chemistry of the Heteronuclear Oxo-Cluster [VPO4]•+: A Model System for the Gas-Phase Oxidation of Small Hydrocarbons

The heteronuclear oxo-cluster [VPO4](•+) is generated via electrospray ionization and investigated with respect to both its electronic structure as well as its gas-phase reactivity toward small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V2O4](•+). As described in previous studies, the latter oxide exhibits no or just minor reactivity toward small hydrocarbons, such as CH4, C2H6, C3H8, n-C4H10, and C2H4, while substitution of one vanadium by a phosphorus atom yields the reactive [VPO4](•+) ion; the latter brings about oxidative dehydrogenation (ODH) of saturated hydrocarbons, e.g., propane and butane as well as oxygen-atom transfer (OAT) to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO4](•+) is determined by IR photodissociation spectroscopy and compared to that of [V2O4](•+). DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorus in terms of C-H bond activation of hydrocarbons by mixed VPO clusters.

Structure of anionic c-type peptide fragments elucidated by IRMPD spectroscopy

In contrast to protonated peptides, collision-induced dissociation of deprotonated peptides is known to yield abundant c- and z-type fragments, in addition to typical a-, b- and y-type ions. Here we investigate the isomeric structures of short anionic c-type peptide fragments using IR photodissociation spectroscopy. As for all N-terminal fragments of deprotonated peptides, an important structural question concerns the site of deprotonation, as no C-terminal COOH group is present in these products. Comparison of the experimental action spectra with spectra computed for several candidate structures suggests that the c1 and c2 ions investigated have linear peptide structures with a C-terminal C(O)NH2 amide group. Competition between deprotonation on the peptide bond nitrogen atom, forming an amidate anion, and on the residue side chain, depending on its gas-phase acidity, is observed.

IR and IR + UV spectroscopy of isolated [Al–AcPheOMe]n+ cluster cations (n = 1, 3)

Singly and triply charged cationic clusters of aluminium and the protected amino acid AcPheOMe are investigated in a supersonic beam by using a combination of a thermic and a laser ablation ion source. For the singly charged species UV- and IR photodissociation spectroscopy is applied. In the case of the triply charged clusters a variant of combined IR + UV spectroscopy is used to obtain information in the NH-stretching region. By comparison with DFT calculations structural assignments are suggested and it turns out that both clusters prefer a helical arrangement with aluminium being aggregated to both carbonyl groups. For the triply charged cluster a globular structure is formed in which aluminium is captured both by the carbonyl groups and the phenyl ring.

Laser Spectroscopic and Theoretical Studies of Encapsulation Complexes of Calix[4]arene

The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH(3), N(2), CH(4), and C(2)H(2) have been investigated via experimental and theoretical methods. The S(1)-S(0) electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser-induced fluorescence (LIF) spectroscopy. The IR spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-rare gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H(2)O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N(2), CH(4), and C(2)H(2) exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H(2)O and NH(3) show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C(2)H(2), show a broad hydrogen-bonded OH stretching band with a peak at ~3160 cm(-1). The analysis of the experimental results, in agreement with the ones resulting from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes (guests inside the host calizarene cavity) with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies, and the nature of the interaction between the C4A host and the various guest species.

Entropy-driven rearrangement of the water network at the hydrated amide group of the trans-formanilide–water cluster in the gas phase

Photoionization-induced rearrangement of the water network in the trans-formanilide 1:4 cluster, FA-(H(2)O)(4), has been investigated by using IR-photodissociation spectroscopy and quantum chemical calculations. The IR spectrum of FA-(H(2)O)(4) in the S(0) state shows that the observed cluster has a cyclic hydrogen-bonded structure where the CO group and the NH group of FA are bridged with four water molecules, consistent with the reported structure [E. G. Robertson, Chem. Phys. Lett., 2000, 325, 299]. However, the corresponding cyclic hydrogen-bonded structure in the D(0) state of [FA-(H(2)O)(4)](+) is a minor product arising from photoionization via the S(1)-S(0) origin of FA-(H(2)O)(4). The dominant product has an extended H-bonded structure, where the intermolecular hydrogen bond between the hydrogen of the OH group of a water molecule and the CO group is dissociated. This is the first observation of a photoionization-induced rearrangement of the water network in [FA-(H(2)O)(4)](+). Through DFT calculations, we conclude that the rearrangement occurs due to entropic effects.

IR spectroscopy on isolated Con(alcohol)m cluster anions (n=1–4,m=1–3): Structures and spin states

Isolated cobalt-alcohol cluster anions containing n=1-4 cobalt and m=1-3 alcohol molecules (alcohol=methanol, ethanol, propanol) are produced in a supersonic beam by using a laser ablation source. By applying IR photodissociation spectroscopy vibrational spectra in the OH stretching region are obtained. Several structures in different spin states are discussed for the (n,m) clusters. In comparison with density functional theory calculations applied to both the Co/alcohol clusters and the naked Co cluster anions, an unambiguous structural assignment is achieved. It turns out that structures are preferred with a maximum number of hydrogen bonds between the OH groups and the Co···Co units. These hydrogen bonds are typical for anionic species leading to an activation of the OH groups which is indicated by large red-shifts of the OH stretching frequencies compared to the naked alcohols. For each (n,m) cluster, the frequency shifts systematically with respect to the different alcohols, but the type of structure is identical for all alcohol ligands. The application of IR spectroscopy turns out to be an ideal tool not only as a probe for structures but also for spin states which significantly influence the predicted OH stretching frequencies.