Optical spectroscopy coupled with mass spectrometry methods
This themed issue reports on recent progress in the fast developing field of spectroscopy of ions by means of mass spectrometry coupled with optical spectroscopy. It focuses on both the experimental and theoretical aspects of this topic.
Photoisomerization action spectroscopy: flicking the protonated merocyanine–spiropyran switch in the gas phase
Molecular ions drifting through buffer gas are exposed to tunable laser light causing a detectable change in their collision cross section and arrival time at the ion detector. The effect can be exploited to obtain action electronic spectra for selected molecular isomers in the gas phase.
Anharmonic simulations of the vibrational spectrum of sulfated compounds: application to the glycosaminoglycan fragment glucosamine 6-sulfate
Anharmonic behavior of sulfated glucosamine resolved by hybrid GVPT2 approach.
Vibrational spectroscopy and theory of Fe2+(CH4)n (n = 1–3)
Vibrational spectroscopy of size selected clusters reveals the extent to which interactions with Fe2+ weaken proximate C–H bonds in methane ligands.
Combining gas phase electron capture and IRMPD action spectroscopy to probe the electronic structure of a metastable reduced organometallic complex containing a non-innocent ligand
Gas-phase reduction of a Zn(II) complex followed by IR spectroscopy shows that the incoming electron is localized on the metal rather than on the ligand.
Bonding of heme FeIII with dioxygen: observation and characterization of an incipient bond
The first observation and characterization of the [heme FeIII–O2]+ complex. Determination of the FeIII–O2 binding energy.
Tandem mass spectrometry and infrared spectroscopy as a tool to identify peptide oxidized residues
Met–Trp oxidized products formed by γ radiolysis and their vibrational signatures.
Diverse mixtures of 2,4-dihydroxy tautomers and O4 protonated conformers of uridine and 2′-deoxyuridine coexist in the gas phase
IRMPD spectroscopy and theoretical studies reveal that a diverse mixture of minor 2,4-dihydroxy and O4 protonated tautomeric conformations of the protonated forms of uridine and 2′-deoxyuridine are populated by ESI.
Vibrational mode assignment of finite temperature infrared spectra using the AMOEBA polarizable force field
The Driven Molecular Dynamics approach has been adapted and associated with the AMOEBA polarizable force field to assign and visualize vibrational modes in infrared spectra obtained by molecular dynamics simulations.
Real time observation of the excimer formation dynamics of a gas phase benzene dimer by picosecond pump–probe spectroscopy
Photoexcitation of a T-shaped benzene dimer provides a sandwiched excimer in 10 ps accompanying a 1000 times faster intracluster vibrational energy redistribution rate than that of the benzene monomer.
Nonlinear effects in infrared action spectroscopy of silicon and vanadium oxide clusters: experiment and kinetic modeling
Nonlinear effects in infrared action spectroscopy are experimentally quantified and successfully modeled for different inorganic clusters.
Hydration of the sulfate dianion in cold nanodroplets: SO42−(H2O)12 and SO42−(H2O)13
The sulfate ion is found to lie at the cluster surface in both cases.
Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations
We report infrared multiple photon dissociation spectra of cryogenically-cooled H2PO4−(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm−1).
UV photodissociation spectroscopy of cryogenically cooled gas phase host–guest complex ions of crown ethers
Crown ethers show a dramatic effect on the electronic spectra and fragmentation patterns of guest species.
Optical properties of prodigiosin and obatoclax: action spectroscopy and theoretical calculations
Action spectroscopy and first principles calculations are performed to characterize the optical properties of prodigiosin, and its sensibility to protonation, counter-ion binding, and isomerization.
On the Ag+–cytosine interaction: the effect of microhydration probed by IR optical spectroscopy and density functional theory
Single water molecule hydration stabilizes two quasi-isoenergetic complexes of cytosine⋯Ag+.
Can far-IR action spectroscopy combined with BOMD simulations be conformation selective?
The combination of conformation selective far-IR/UV double resonance spectroscopy with Born–Oppenheimer molecular dynamics (BOMD) simulations is presented here for the structural characterization of the Ac-Phe-Pro-NH2 peptide in the far-infrared spectral domain, i.e. for radiation below 800 cm−1.
Ultraviolet photodissociation action spectroscopy of gas-phase protonated quinoline and isoquinoline cations
Gas-phase two-photon UV action spectra of protonated quinoline and isoquinoline cations are reported revealing two broad, vibrationally-structured electronic bands and multiple photoproduct channels.
Infrared multiple photon dissociation spectrum of protonated bis(2-methoxyethyl) ether obtained with a tunable CO2 laser
A moderate-resolution infrared multiple photon dissociation (IRMPD) spectrum of protonated bis(2-methoxyethyl) ether (diglyme) was obtained using a grating-tuned CO2 laser.
Serine O-sulfation probed by IRMPD spectroscopy
The gas phase structures of (de)protonated O-sulfoserine ions have been revealed by infrared multiple photon dissociation (IRMPD) spectroscopy and computations.
An infrared spectroscopic and theoretical study on (CH3)3N–H+–(H2O)n, n = 1–22: highly polarized hydrogen bond networks of hydrated clusters
Highly polarized water networks are found in the micro hydaration of protonated trimethylamine.
A comprehensive study of cold protonated tyramine: UV photodissociation experiments and ab initio calculations
Excited state properties of cold protonated ions are revealed by a combination of laser spectroscopy and ab initio calculations.
Gas-phase structure and reactivity of the keto tautomer of the deoxyguanosine radical cation
Gas-phase IR spectroscopy, ion–molecule reactions, collision-induced dissociation and computational chemistry in combination form a powerful tool to gain insights into the structure of one-electron oxidised guanine in DNA and its resultant chemistry.
Spectroscopic studies of kinetically trapped conformations in the gas phase: the case of triply protonated bradykinin
We explore conformational space of triply protonated bradykinin. Three conformational families are mobility-separated and spectroscopically characterized. Kinetically trapped structures are identified via annealing.
Characterizing gaseous peptide structure with action-EET and simulated annealing
Distance-sensitive energy transfer and molecular dynamics are used to generate experimentally corroborated structures for peptides in the gas phase.
Electronic structure and conformational flexibility of D-cycloserine
The conformational flexibility effect on the valence and core electronic structures of D-cycloserine.
The Soret absorption band of isolated chlorophyll a and b tagged with quaternary ammonium ions
The true colors of chlorophyll a and b, isolated in vacuo, are revealed from a combination of gas-phase ion spectroscopy and TD-DFT calculations.
Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy
Zinc and cadmium dications bind cysteine in tridentate structures at the amine and carbonyl groups and deprotonated sulfur atom.
Diastereo-specific conformational properties of neutral, protonated and radical cation forms of (1R,2S)-cis- and (1R,2R)-trans-amino-indanol by gas phase spectroscopy
The effects of ionisation and protonation on the geometric and electronic structure of a prototypical aromatic amino-alcohol with two chiral centres are revealed by IR and UV spectroscopy.
Gas-phase VUV photoionisation and photofragmentation of the silver deuteride nanocluster [Ag10D8L6]2+ (L = bis(diphenylphosphino)methane). A joint experimental and theoretical study
The VUV photoionisation and photofragmentation of a mass-selected, ligated silver deuteride nanocluster was studied.
Charge transfer in MOH(H2O)+ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions
The hydroxide frequency in MOH(H2O)+ is a sensitive probe of charge transfer.
Guanine tetrads: an IRMPD spectroscopy, energy resolved SORI-CID, and computational study of M(9-ethylguanine)4+ (M = Li, Na, K, Rb, Cs) in the gas phase
The electrostatic potential map of the neutral guanine tetrad showing the negative hole in the centre.
A pulsed uniform Laval expansion coupled with single photon ionization and mass spectrometric detection for the study of large molecular aggregates
The combination of Laval expansions with single photon VUV ionization and linear time of flight mass spectrometry allows one to study weakly-bound molecular aggregates under equilibrium conditions.
UV spectroscopy of cold ions as a probe of the protonation site
Where does the proton go?
IR spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity of the NH3+–π interaction
Calculations and IR spectra reveal the effects of anharmonicity and dispersion on the cation–π interaction in this prototypical neurotransmitter.
Photodissociation dynamics of ethanethiol in clusters: complementary information from velocity map imaging, mass spectrometry and calculations
We investigate the solvent effects on photodissociation dynamics of the S–H bond in ethanethiol CH3CH2SH (EtSH).
Action spectroscopy of a protonated peptide in the ultraviolet range
Action spectroscopy of substance P, a model undecapeptide, has been probed from 5.2 eV to 20 eV.
About this collection
This themed issue reports recent progress in the fast developing field of spectroscopy of ions by means of mass spectrometry coupled with optical spectroscopy, focussing on both the experimental and theoretical aspects of this topic. The guest editor for this themed issue is Anne Zehnacker (University of Paris-Sud, France).