Infrared spectra of SinH4n-1+ ions (n = 2-8): inorganic H-(Si-H)n-1 hydride wires of penta-coordinated Si in 3c-2e and charge-inverted hydrogen bonds.

SinHm+ cations are important constituents in silane plasmas and astrochemical environments. Protonated disilane (Si2H7+) was shown to have a symmetric three-centre two-electron (3c-2e) Si-H-Si bond that can also be considered as a strong ionic charge-inverted hydrogen bond with polarity Siδ+-Hδ--Siδ+. Herein, we extend our previous work to larger SinH4n-1+ cations, formally resulting from adding SiH4 molecules to a SiH3+ core. Infrared spectra of size-selected SinH4n-1+ ions (n = 2-8) produced in a cold SiH4/H2/He plasma expansion are analysed in the SiH stretch range by complementary dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ) to reveal their bonding characteristics and cluster growth. The ions with n = 2-4 form a linear inorganic H-(Si-H)n hydride wire with adjacent Si-H-Si 3c-2e bridges, whose strength decreases with n, as evident from their characteristic and strongly IR active SiH stretch fundamentals in the range 1850-2100 cm-1. These 3c-2e bonds result from the lowest-energy valence orbitals, and their high stability arises from their delocalization along the whole hydride wire. For SinH4n-1+ with n ≥ 5, the added SiH4 ligands form weak van der Waals bonds to the Si4H19+ chain. Significantly, because the SinH4n-1+ hydride wires are based on penta-coordinated Si atoms leading to supersaturated hydrosilane ions, analogous wires cannot be formed by isovalent carbon.

Internal Energy Dependence of the Pyrrole Dimer Cation Structures Formed in a Supersonic Plasma Expansion: Charge-Resonance and Hydrogen-Bonded Isomers.

The structures of the pyrrole dimer cation (Py2+) formed in an electron-ionization-driven supersonic plasma expansion of Py seeded in Ar or N2 are probed as a function of its internal energy by infrared photodissociation (IRPD) spectroscopy in a tandem mass spectrometer. The IRPD spectra recorded in the CH and NH stretch ranges are analyzed by dispersion-corrected density functional theory (DFT) calculations at the B3LYP-D3/aug-cc-pVTZ level. The spectra of the cold Ar/N2-tagged Py2+ clusters, Py2+Ln (n = 1-5 for Ar, n = 1 for N2), indicate the exclusive formation of the most stable antiparallel π-stacked Py2+ structure under cold conditions, which is stabilized by charge-resonance interaction. The bare Py2+ dimers produced in the ion source have higher internal energy, and the observation of additional transitions in their IRPD spectra suggests a minor population of less stable hydrogen-bonded isomers composed of heterocyclic Py/Py+ structures formed after intramolecular H atom transfer and ring opening. These intermolecular isomers differ from the chemically bonded structures proposed earlier in the analysis of IRPD spectra of Py2+ generated by VUV ionization of neutral Pyn clusters.

Hydration Rearrangement in the 4-Aminobenzonitrile-(H2 O)2 Cluster Induced by Photoionization: The Effect of Solvent-Solvent Interactions.

The interplay between solute-solvent and solvent-solvent interactions plays an essential role in solvation dynamics that has important effects on the mechanism and dynamics of chemical reactions in solution. In this study, the rearrangement of the hydration shell induced by photoionization of a solute molecule is probed in a state- and isomer-specific manner by resonant multiphoton ionization detected IR spectroscopy of the prototypical 4-aminobenzonitrile-(H2 O)2 cluster produced in a molecular beam. IR spectra reveal that the water molecules form a cyclic solvent network around the CN group in the initial neutral state (S0 ). Different from the singly-hydrated cluster, in which either the CN or the NH2 group is hydrated, hydration of the NH2 group is not observed in the dihydrated cluster. IR spectra obtained after ionizing the solute molecule into the cation ground state (D0 ) exhibit features ascribed to both NH-bound and CN-bound isomers, indicating that water molecules migrate from the CN to the NH site upon ionization with a yield depending on the ionization excess energy. Analysis of the IR spectra as a function of the excess energy shows that migration produces two different NH2 solvated structures, namely (i) the most stable structure in which both N-H bonds are singly hydrated and (ii) the second most stable isomer in which one of the N-H bonds is hydrated by a H-bonded (H2 O)2 dimer. The product branching ratio of the two isomers depends on the excess energy. The role of the water-water interaction in the hydration rearrangement is discussed based on the potential energy landscape. Solvation dynamics plays an important role in reaction mechanisms in the condensed phase, where not only solute-solvent solvation but also solvent-solvent interactions have a significant influence on the dynamics. Thus, the investigation of solvation dynamics at the molecular level substantially contributes to our understanding of the reaction mechanism. In this study, the dihydrated cluster of 4ABN was utilized as a model for the first solvation layer to elucidate solvent motions induced by ionization of the solute and the role of W-W interactions for the solvent relaxation.

Infrared spectrum of the 1-cyanoadamantane cation: evidence of hydrogen transfer and cage-opening upon ionization.

The radical cations of diamondoids are important intermediates in their functionalization reactions and are also candidates as carriers for astronomical absorption and emission features. Although neutral diamondoids have been studied extensively, information regarding their radical cations is largely lacking, particularly for functionalized diamondoid derivatives. Herein, we characterize the structure of the 1-cyanoadamantane radical cation (C10H15CN+, AdCN+) using infrared photodissociation (IRPD) spectroscopy of mass selected AdCN+N2 clusters in the XH stretch range (2400-3500 cm-1) and dispersion-corrected density functional theory calculations (B3LYP-D3BJ/cc-pVTZ). A group of three distinct CH stretch bands are observed in the 2800-3000 cm-1 range, in addition to a highly redshifted absorption at 2580 cm-1 attributed to the acidic CH proton predicted by calculations. An unexpected broad absorption peaking at 3320 cm-1 is also detected and assigned to an NH stretch mode based on its width and frequency. Calculations indicate that hydrogen atom transfer (HAT) from the adamantyl cage (C10H15, Ady) to the N atom of the CN group yields lower energy structures, with an open-cage isomer exhibiting such hydrogen transfer being the global minimum on the potential energy surface. The energy barriers involved in the formation of this open-cage isomer are also lower than those calculated for generation of the analogous open-cage 1-amantadine cation isomer which has previously been identified by IRPD. The combined consideration of IRPD spectra and calculations indicates a major population of the nascent canonical closed-cage isomer and a smaller population of the global minimum isomer featuring both cage-opening and hydrogen transfer.

Microhydrated clusters of a pharmaceutical drug: infrared spectra and structures of amantadineH+(H2O)n.

Solvation of pharmaceutical drugs has an important effect on their structure and function. Analysis of infrared photodissociation spectra of amantadineH+(H2O)n=1-4 clusters in the sensitive OH, NH, and CH stretch range by quantum chemical calculations (B3LYP-D3/cc-pVTZ) provides a first impression of the interaction of this pharmaceutically active cation with water at the molecular level. The size-dependent frequency shifts reveal detailed information about the acidity of the protons of the NH3+ group of N-protonated amantadineH+ (AmaH+) and the strength of the NH⋯O and OH⋯O hydrogen bonds (H-bonds) of the hydration network. The preferred cluster growth begins with sequential hydration of the NH3+ group by NH⋯O ionic H-bonds (n = 1-3), followed by the extension of the solvent network through OH⋯O H-bonds. However, smaller populations of cluster isomers with an H-bonded solvent network and free N-H bonds are already observed for n ≥ 2, indicating the subtle competition between noncooperative ion hydration and cooperative H-bonding. Interestingly, cyclic water ring structures are identified for n ≥ 3, each with two NH⋯O and two OH⋯O H-bonds. Despite the increasing destabilization of the N-H proton donor bonds upon gradual hydration, no proton transfer to the (H2O)n solvent cluster is observed up to n = 4. In addition to ammonium cluster ions, a small population of microhydrated iminium isomers is also detected, which is substantially lower for the hydrophilic H2O than for the hydrophobic Ar environment.

Microhydration of the adamantane cation: intracluster proton transfer to solvent in [Ad(H2O)n=1-5]+ for n ≥ 3.

Radical cations of diamondoids are important intermediates in their functionalization reactions in polar solvents. To explore the role of the solvent at the molecular level, we characterize herein microhydrated radical cation clusters of the parent molecule of the diamondoid family, adamantane (C10H16, Ad), by infrared photodissociation (IRPD) spectroscopy of mass-selected [Ad(H2O)n=1-5]+ clusters. IRPD spectra of the cation ground electronic state recorded in the CH/OH stretch and fingerprint ranges reveal the first steps of this fundamental H-substitution reaction at the molecular level. Analysis of size-dependent frequency shifts with dispersion-corrected density functional theory calculations (B3LYP-D3/cc-pVTZ) provides detailed information about the acidity of the proton of Ad+ as a function of the degree of hydration, the structure of the hydration shell, and the strengths of the CH⋯O and OH⋯O hydrogen bonds (H-bonds) of the hydration network. For n = 1, H2O strongly activates the acidic C-H bond of Ad+ by acting as a proton acceptor in a strong CH⋯O ionic H-bond with cation-dipole configuration. For n = 2, the proton is almost equally shared between the adamantyl radical (C10H15, Ady) and the (H2O)2 dimer in a strong C⋯H⋯O ionic H-bond. For n ≥ 3, the proton is completely transferred to the H-bonded hydration network. The threshold for this size-dependent intracluster proton transfer to solvent is consistent with the proton affinities of Ady and (H2O)n and confirmed by collision-induced dissociation experiments. Comparison with other related microhydrated cations reveals that the acidity of the CH proton of Ad+ is in the range of strongly acidic phenol+ but lower than for cationic linear alkanes such as pentane+. Significantly, the presented IRPD spectra of microhydrated Ad+ provide the first spectroscopic molecular-level insight of the chemical reactivity and reaction mechanism of the important class of transient diamondoid radical cations in aqueous solution.

Photochemical properties of a potential interstellar dust precursor: the electronic spectrum of Si3O2.

Silicon oxide compounds are considered as precursors for silicon-based interstellar dust grains which consist mainly of silica and silicates. Knowledge of their geometric, electronic, optical, and photochemical properties provides crucial input for astrochemical models describing the evolution of dust grains. Herein, we report the optical spectrum of mass-selected Si3O2+ cations recorded in the 234-709 nm range by means of electronic photodissociation (EPD) in a quadrupole/time-of-flight tandem mass spectrometer coupled to a laser vaporization source. The EPD spectrum is observed predominantly in the lowest-energy fragmentation channel corresponding to Si2O+ (loss of SiO), while the higher-energy Si+ channel (loss of Si2O2) provides only a minor contribution. The EPD spectrum exhibits two weaker unresolved bands A and B near 26 490 and 34 250 cm-1 (377.5 and 292 nm) and a strong transition C with a band origin at 36 914 cm-1 (270.9 nm) which shows vibrational fine structure. Analysis of the EPD spectrum is guided by complementary time-dependent density functional theory (TD-DFT) calculations at the UCAM-B3LYP/cc-pVTZ and UB3LYP/cc-pVTZ levels to determine structures, energies, electronic spectra, and fragmentation energies of the lowest-energy isomers. The cyclic global minimum structure with C2v symmetry determined previously by infrared spectroscopy can explain the EPD spectrum well, with assignments of bands A-C to transitions from the 2A1 ground electronic state (D0) into the 4th, 9th, and 11th excited doublet states (D4,9,11), respectively. The vibronic fine structure of band C is analyzed by Franck-Condon simulations, which confirm the isomer assignment. Significantly, the presented EPD spectrum of Si3O2+ corresponds to the first optical spectrum of any polyatomic SinOm+ cation.

Hydration-induced protomer switching in p-aminobenzoic acid studied by cold double ion trap infrared spectroscopy.

Para-Aminobenzoic acid (PABA) is a benchmark molecule to study solvent-induced proton site switching. Protonation of the carboxy and amino groups of PABA generates O- and N-protomers of PABAH+, respectively. Ion mobility mass spectrometry (IMS) and infrared photodissociation (IRPD) studies have claimed that the O-protomer most stable in the gas phase is converted to the N-protomer most stable in solution upon hydration with six water molecules in the gas-phase cluster. However, the threshold size has remained ambiguous because the arrival time distributions in the IMS experiments exhibit multiple peaks. On the other hand, IRPD spectroscopy could not detect the N-protomer for smaller hydrated clusters because of broad background due to annealing required to reduce kinetic trapping. Herein, we report the threshold size for O → N protomer switching without ambiguity using IR spectroscopy in a double ion trap spectrometer from 1300 to 1800 cm-1. The pure O-protomer is prepared by electrospray, and size-specific hydrated clusters are formed in a reaction ion trap. The resulting clusters are transferred into a second cryogenic ion trap and the distribution of O- and N-protomers is determined by mid-IR spectroscopy without broadening. The threshold to promote O → N protomer switching is indeed five water molecules. It is smaller than the value reported previously, and as a result, its pentahydrated structure does not support the Grotthuss mechanism proposed previously. The extent of O → N proton transfer is evaluated by collision-assisted stripping IR spectroscopy, and the N-protomer population increases with the number of water molecules. This result is consistent with the dominant population of the N-protomer in aqueous solution.

Microhydration of the Pyrrole Cation (Py+) Revealed by IR Spectroscopy: Ionization-Induced Rearrangement of the Hydrogen-Bonded Network of Py+(H2O)2.

Microhydration of heterocyclic aromatic molecules can be an appropriate fundamental model to shed light on intermolecular interactions and functions of macromolecules and biomolecules. We characterize herein the microhydration process of the pyrrole cation (Py+) by infrared photodissociation (IRPD) spectroscopy and dispersion-corrected density functional theory calculations (B3LYP-D3/aug-cc-pVTZ). Analysis of IRPD spectra of mass-selected Py+(H2O)2 and its cold Ar-tagged cluster in the NH and OH stretch range combined with geometric parameters of intermolecular structures, binding energies, and natural atomic charge distribution provides a clear picture of the growth of the hydration shell and cooperativity effects. Py+(H2O)2 is formed by stepwise hydration of the acidic NH group of Py+ by a hydrogen-bonded (H2O)2 chain with NH···OH···OH configuration. In this linear H-bonded hydration chain, strong cooperativity, mainly arising from the positive charge, strengthens both the NH···O and OH···O H-bonds with respect to those of Py+H2O and (H2O)2, respectively. The linear chain structure of the Py+(H2O)2 cation is discussed in terms of the ionization-induced rearrangement of the hydration shell of the neutral Py(H2O)2 global minimum characterized by the so-called "σ-π bridge structure" featuring a cyclic NH···OH···OH···π H-bonded network. Emission of the π electron from Py by ionization generates a repulsive interaction between the positive π site of Py+ and the π-bonded OH hydrogen of (H2O)2, thereby breaking this OH···π hydrogen bond and driving the hydration structure toward the linear chain motif of the global minimum on the cation potential.

Electronic and vibrational spectroscopies of aromatic clusters with He in a supersonic jet: The case of neutral and cationic phenol-Hen (n = 1 and 2).

Van der Waals clusters composed of He and aromatic molecules provide fundamental information about intermolecular interactions in weakly bound systems. In this study, phenol-helium clusters (PhOH-Hen with n ≤ 2) are characterized for the first time by UV and IR spectroscopies. The S1 ← S0 origin and ionization energy both show small but additive shifts, suggesting π-bound structures of these clusters, a conclusion supported by rotational contour analyses of the S1 origin bands. The OH stretching vibrations of the PhOH moiety in the clusters match with those of bare PhOH in both the S0 and D0 states, illustrating the negligible perturbation of the He atoms on the molecular vibration. Matrix shifts induced by He attachment are discussed based on the observed band positions with the help of complementary quantum chemical calculations. For comparison, the UV and ionization spectra of PhOH-Ne are reported as well.

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N2 , and H2 O.

Radical cations of diamondoids, a fundamental class of very stable cyclic hydrocarbon molecules, play an important role in their functionalization reactions and the chemistry of the interstellar medium. Herein, we characterize the structure, energy, and intermolecular interaction of clusters of the amantadine radical cation (Ama+ , 1-aminoadamantane) with solvent molecules of different interaction strength by infrared photodissociation (IRPD) spectroscopy of mass-selected Ama+ Ln clusters, with L=Ar (n≤3) and L=N2 and H2 O (n=1), and dispersion-corrected density functional theory calculations (B3LYP-D3/cc-pVTZ). Three isomers of Ama+ generated by electron ionization are identified by the vibrational properties of their rather different NH2 groups. The ligands bind preferentially to the acidic NH2 protons, and the strength of the NH…L ionic H-bonds are probed by the solvation-induced red-shifts in the NH stretch modes. The three Ama+ isomers include the most abundant canonical cage isomer (I) produced by vertical ionization, which is separated by appreciable barriers from two bicyclic distonic iminium ions obtained from cage-opening (primary radical II) and subsequent 1,2 H-shift (tertiary radical III), the latter of which is the global minimum on the Ama+ potential energy surface. The effect of solvation on the energetics of the potential energy profile revealed by the calculations is consistent with the observed relative abundance of the three isomers. Comparison to the adamantane cation indicates that substitution of H by the electron-donating NH2 group substantially lowers the barriers for the isomerization reaction.

Cation-π Interactions between a Noble Metal and a Polyfunctional Aromatic Ligand: Ag+ (benzylamine).

The structure of an isolated Ag+ (benzylamine) complex is investigated by infrared multiple photon dissociation (IRMPD) spectroscopy complemented with quantum chemical calculations of candidate geometries and their vibrational spectra, aiming to ascertain the role of competing cation-N and cation-π interactions potentially offered by the polyfunctional ligand. The IRMPD spectrum has been recorded in the 800-1800 cm-1 fingerprint range using the IR free electron laser beamline coupled with an FT-ICR mass spectrometer at the Centre Laser Infrarouge d'Orsay (CLIO). The resulting IRMPD pattern points toward a chelate coordination (N-Ag+ -π) involving both the amino nitrogen atom and the aromatic π-system of the phenyl ring. The gas-phase reactivity of Ag+ (benzylamine) with a neutral molecular ligand (L) possessing either an amino/aza functionality or an aryl group confirms N- and π-binding affinity and suggests an augmented silver coordination in the product adduct ion Ag + ( benzylamine ) ( L ) .

Microsolvation of H2O+, H3O+, and CH3OH2+ by He in a cryogenic ion trap: structure of solvation shells.

Due to the weak interactions of He atoms with neutral molecules and ions, the preparation of size-selected clusters for the spectroscopic characterization of their structures, energies, and large amplitude motions is a challenging task. Herein, we generate H2O+Hen (n ≤ 9) and H3O+Hen (n ≤ 5) clusters by stepwise addition of He atoms to mass-selected ions stored in a cryogenic 22-pole ion trap held at 5 K. The population of the clusters as a function of n provides insight into the structure of the first He solvation shell around these ions given by the anisotropy of the cation-He interaction potential. To rationalize the observed cluster size distributions, the structural, energetic, and vibrational properties of the clusters are characterized by ab initio calculations up to the CCSD(T)/aug-cc-pVTZ level. The cluster growth around both the open-shell H2O+ and closed-shell H3O+ ions begins by forming nearly linear and equivalent OH⋯He hydrogen bonds (H-bonds) leading to symmetric structures. The strength of these H-bonds decreases slightly with n due to noncooperative three-body induction forces and is weaker for H3O+ than for H2O+ due to both enhanced charge delocalization and reduced acidity of the OH protons. After filling all available H-bonded sites, addition of further He ligands around H2O+ (n = 3-4) occurs at the electrophilic singly occupied 2pz orbital of O leading to O⋯He p-bonds stabilized by induction and small charge transfer from H2O+ to He. As this orbital is filled for H3O+, He atoms occupy in the n = 4-6 clusters positions between the H-bonded He atoms, leading to a slightly distorted regular hexagon ring for n = 6. Comparison between H3O+Hen and CH3OH2+Hen illustrates that CH3 substitution substantially reduces the acidity of the OH protons, so that only clusters up to n = 2 can be observed. The structure of the solvation sub-shells is visible in both the binding energies and the predicted vibrational OH stretch and bend frequencies.

Infrared spectra and structures of protonated amantadine isomers: detection of ammonium and open-cage iminium ions.

The protonated form of amantadine (1-C10H15NH2, Ama), the amino derivative of adamantane (C10H16, Ada), is a wide-spread antiviral and anti-Parkinsonian drug and plays a key role in many pharmaceutical processes. Recent studies reveal that the adamantyl cage (C10H15) of Ama can open upon ionization leading to distonic bicyclic iminium isomers, in addition to the canonical nascent Ama+ isomer. Herein, we study protonation of Ama using infrared photodissociation spectroscopy (IRPD) of Ar-tagged ions and density functional theory calculations to characterize cage and open-cage isomers of AmaH+ and the influence of the electron-donating NH2 group on the cage-opening reaction potential. In addition to the canonical ammonium isomer (AmaH+(I)) with an intact adamantyl cage, we identify at least one slightly less stable protonated bicyclic iminium ion (AmaH+(II)). While the ammonium ion is generated by protonation of the basic NH2 group, AmaH+(II) is formally formed by H addition to a distonic bicyclic iminium ion produced upon ionization of Ama and subsequent cage opening.

Collision-assisted stripping for determination of microsolvation-dependent protonation sites in hydrated clusters by cryogenic ion trap infrared spectroscopy: the case of benzocaineH+(H2O)n.

The protonation site of molecules can be varied by their surrounding environment. Gas-phase studies, including the popular techniques of infrared spectroscopy and ion mobility spectrometry, are a powerful tool for the determination of protonation sites in solvated clusters but often suffer from inherent limits for larger hydrated clusters. Here, we present collision-assisted stripping infrared (CAS-IR) spectroscopy as a new technique to overcome these problems and apply it in a proof-of-principle experiment to hydrated clusters of protonated benzocaine (H+BC), which shows protonation-site switching depending on the degree of hydration. The most stable protomer of H+BC in the gas phase (O-protonated) is interconverted into its most stable protomer in aqueous solution (N-protonated) upon hydration with three water molecules. CAS-IR spectroscopy enables us to unambiguously assign protonation sites and quantitatively determine the relative abundance of various protomers.

Comparison of Conventional and Nonconventional Hydrogen Bond Donors in Au- Complexes.

Although gold has become a well-known nonconventional hydrogen bond acceptor, interactions with nonconventional hydrogen bond donors have been largely overlooked. In order to provide a better understanding of these interactions, two conventional hydrogen bonding molecules (3-hydroxytetrahydrofuran and alaninol) and two nonconventional hydrogen bonding molecules (fenchone and menthone) were selected to form gas-phase complexes with Au-. The Au-[M] complexes were investigated using anion photoelectron spectroscopy and density functional theory. Au-[fenchone], Au-[menthone], Au-[3-hydroxyTHF], and Au-[alaninol] were found to have vertical detachment energies of 2.71 ± 0.05, 2.76 ± 0.05, 3.01 ± 0.03, and 3.02 ± 0.03 eV, respectively, which agree well with theory. The photoelectron spectra of the complexes resemble the spectrum of Au- but are blueshifted due to the electron transfer from Au- to M. With density functional theory, natural bond orbital analysis, and atoms-in-molecules analysis, we were able to extend our comparison of conventional and nonconventional hydrogen bonding to include geometric and electronic similarities. In Au-[3-hydroxyTHF] and Au-[alaninol], the hydrogen bonding comprised of Au-···HO as a strong, primary hydrogen bond, with secondary stabilization by weaker Au-···HN or Au-···HC hydrogen bonds. Interestingly, the Au-···HC bonds in Au-[fenchone] and Au-[menthone] can be characterized as hydrogen bonds, despite their classification as nonconventional hydrogen bond donors.

Near-Infrared Spectrum of the First Excited State of Au2.

Au2 + is a simple but crucial model system for understanding the diverse catalytic activity of gold. While the Au2 + ground state (X2 Σg + ) is understood reasonably well from mass spectrometry and computations, no spectroscopic information is available for its first excited state (A2 Σu + ). Herein, we present the vibrationally resolved electronic spectrum of this state for cold Ar-tagged Au2 + cations. This exceptionally low-lying and well isolated A2 Σ(u) + ←X2 Σ(g) + transition occurs in the near-infrared range. The observed band origin (5738 cm-1 , 1742.9 nm, 0.711 eV) and harmonic Au-Au and Au-Ar stretch frequencies (201 and 133 cm-1 ) agree surprisingly well with those predicted by standard time-dependent density functional theory calculations. The linearly bonded Ar tag has little impact on either the geometric or electronic structure of Au2 + , because the Au2 + ⋅⋅⋅Ar bond (∼0.4 eV) is much weaker than the Au-Au bond (∼2 eV). As a result of 6 s←5d excitation of an electron from the antibonding σu * orbital (HOMO-1) into the bonding σg orbital (SOMO), the Au-Au bond contracts substantially (by 0.1 Å).

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.

Infrared action spectroscopy of nitrous oxide on cationic gold and cobalt clusters.

Understanding the catalytic decomposition of nitrous oxide on finely divided transition metals is an important environmental issue. In this study, we present the results of a combined infrared action spectroscopy and quantum chemical investigation of molecular N2O binding to isolated Aun+ (n ≤ 7) and Con+ (n ≤ 5) clusters. Infrared multiple-photon dissociation spectra have been recorded in the regions of both the N[double bond, length as m-dash]O (1000-1400 cm-1) and N[double bond, length as m-dash]N (2100-2450 cm-1) stretching modes of nitrous oxide. In the case of Aun+ clusters only the ground electronic state plays a role, while the involvement of energetically low-lying excited states in binding to the Con+ clusters cannot be ruled out. There is a clear preference for N-binding to clusters of both metals but some O-bound isomers are observed in the case of smaller Con(N2O)+ clusters.

Interaction of Alkali Ions with Flavins: Infrared and Optical Spectra of Metal-Riboflavin Complexes.

Flavin compounds are of great interest in biochemistry because of their diverse functions in catalytic and photochemical processes. The intrinsic optical properties of flavins depend sensitively on their environment such as complexation with metal ions. Herein, we characterize the interaction of alkali metal ions (M+) with riboflavin (RF, vitamin B2). To this end, two different experimental spectroscopic approaches are employed to determine the structural, vibrational, energetic, and optical properties of M+RF complexes by comparison with density functional theory (DFT) calculations at the PBE0/cc-pVDZ level. First, infrared multiple photon dissociation (IRMPD) spectra recorded at room temperature demonstrate that M+ binds to one of the two available nucleophilic carbonyl groups (CO2, CO4) of RF, denoted O2 and O4+ isomers, as revealed by characteristic shifts of the CO stretch modes upon metalation. Second, the optical spectrum of K+RF is recorded between 428 and 529 nm in a cryogenic ion trap held at 6 K by visible photodissociation (VISPD). Analysis of the VISPD spectrum by time-dependent DFT calculations coupled to Franck-Condon simulations demonstrates that in fact only the O2 isomer of M+RF is formed by electrospray ionization, while the spectroscopic signatures of the O4+ isomer are absent. The VISPD spectrum is attributed to the S1 ← S0 (ππ*) transition of the O2 isomer, which is calculated to be much more stable than the O4+ isomer because of additional multiple interactions of M+ with the OH groups of the ribityl (sugar) side chain attached at N10 of RF. In contrast, there is no evidence for the presence of the O4+ isomer, in which M+ forms a chelate complex, with M+ binding to both O4 and N5. A comparison between RF (ribityl at N10) and lumiflavin (LF and CH3 at N10) reveals the drastic effects of the side chain on the structural, energetic, and optical properties of the flavin interaction with metal ions. While for M+LF the O2 and O4+ isomers are close in energy and both observed experimentally, for M+RF the O2 isomer is strongly favored due to the additional interaction with the side chain. Although the S1 energies of M+RF(O2) and M+LF(O2) are quite similar, because the ππ* transition is localized on the same isoalloxazine chromophore for both flavins, the vibrational structures are strongly different because the soft bending potential for the M+···flavin interaction is strongly affected by the ribityl side chain at N10. In contrast to H+RF, which prefers protonation at N1, steric repulsion of the larger M+ ions with the ribityl side chain prevents metalation at N1, leading to the formation of the O2 global minimum.