Structural characterization of electron-induced proton transfer in the formic acid dimer anion, (HCOOH)2-, with vibrational and photoelectron spectroscopies.

The (HCOOH)(2) anion, formed by electron attachment to the formic acid dimer (FA(2)), is an archetypal system for exploring the mechanics of the electron-induced proton transfer motif that is purported to occur when neutral nucleic acid base-pairs accommodate an excess electron [K. Aflatooni, G. A. Gallup, and P. D. Burrow, J. Phys. Chem. A 102, 6205 (1998); J. H. Hendricks, S. A. Lyapustina, H. L. de Clercq, J. T. Snodgrass, and K. H. Bowen, J. Chem Phys. 104, 7788 (1996); C. Desfrancois, H. Abdoul-Carime, and J. P. Schermann, ibid. 104, 7792 (1996)]. The FA(2) anion and several of its H∕D isotopologues were isolated in the gas phase and characterized using Ar-tagged vibrational predissociation and electron autodetachment spectroscopies. The photoelectron spectrum of the FA(2) anion was also recorded using velocity-map imaging. The resulting spectroscopic information verifies the equilibrium FA(2)(-) geometry predicted by theory which features a symmetrical, double H-bonded bridge effectively linking together constituents that most closely resemble the formate ion and a dihydroxymethyl radical. The spectroscopic signatures of this ion were analyzed with the aid of calculated anharmonic vibrational band patterns.

[1]  Andrew F. DeBlase,et al.  Unraveling the Anomalous Solvatochromic Response of the Formate Ion Vibrational Spectrum: An Infrared, Ar-Tagging Study of the HCO2¯, DCO2¯, and HCO2¯·H2O Ions , 2011 .

[2]  J. Leszczynski,et al.  Low-energy-barrier proton transfer induced by electron attachment to the guanine...cytosine base pair. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[3]  Mark A. Johnson,et al.  Survey of Ar-tagged predissociation and vibrationally mediated photodetachment spectroscopies of the vinylidene anion, C2H2-. , 2010, The journal of physical chemistry. A.

[4]  R. T. Skodje,et al.  Infrared spectra of SF6(-) x HCOOH x Ar(n) (n = 0-2): infrared triggered reaction and Ar-induced reactive inhibition. , 2009, The Journal of chemical physics.

[5]  Holger Schneider,et al.  Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state. , 2009, The Journal of chemical physics.

[6]  J. Leszczynski,et al.  Valence anions of 9-methylguanine-1-methylcytosine complexes. Computational and photoelectron spectroscopy studies. , 2009, Journal of the American Chemical Society.

[7]  Ben M. Elliott,et al.  Photoelectron imaging study of vibrationally mediated electron autodetachment in the type I isomer of the water hexamer anion , 2008 .

[8]  A. Sanov,et al.  Photoelectron imaging of negative ions , 2008 .

[9]  J. Roscioli,et al.  Quantum Structure of the Intermolecular Proton Bond , 2007, Science.

[10]  M. Allan.  Electron collisions with formic acid monomer and dimer. , 2007, Physical review letters.

[11]  Maciej Gutowski,et al.  DNA strand breaks induced by concerted interaction of H radicals and low-energy electrons , 2005 .

[12]  Maciej Gutowski,et al.  Anion of the formic acid dimer as a model for intermolecular proton transfer induced by a pi* excess electron. , 2005, The Journal of chemical physics.

[13]  M. Gutowski,et al.  AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions. , 2005, Journal of the American Chemical Society.

[14]  H. Schneider,et al.  An infrared investigation of the (CO2)n- clusters: core ion switching from both the ion and solvent perspectives. , 2005, The journal of physical chemistry. A.

[15]  D. Hurtmans,et al.  Jet-cooled and room temperature FTIR spectra of the dimer of formic acid in the gas phase , 2004 .

[16]  J. Nilles,et al.  Barrier-free proton transfer in anionic complex of thymine with glycine , 2004 .

[17]  Pierre Cloutier,et al.  DNA strand breaks induced by 0-4 eV electrons: the role of shape resonances. , 2004, Physical review letters.

[18]  G. Renger,et al.  Coupling of electron and proton transfer in oxidative water cleavage in photosynthesis. , 2004, Biochimica et biophysica acta.

[19]  M. Sevilla,et al.  Density functional theory studies of electron interaction with DNA: can zero eV electrons induce strand breaks? , 2003, Journal of the American Chemical Society.

[20]  J. Rak,et al.  Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment , 2002 .

[21]  Alexei Ossadtchi,et al.  Reconstruction of Abel-transformable images: The Gaussian basis-set expansion Abel transform method , 2002 .

[22]  Piotr Skurski,et al.  Mechanism for Damage to DNA by Low-Energy Electrons † , 2002 .

[23]  C. Freidhoff,et al.  Anion solvation at the microscopic level: Photoelectron spectroscopy of the solvated anion clusters, NO−(Y)n, where Y=Ar, Kr, Xe, N2O, H2S, NH3, H2O, and C2H4(OH)2 , 2002 .

[24]  Eyal Nir,et al.  Pairing of isolated nucleic-acid bases in the absence of the DNA backbone , 2022 .

[25]  O. Dopfer,et al.  High-resolution spectroscopy of cluster ions. , 2000, Chemical reviews.

[26]  Weber,et al.  Isolating the spectroscopic signature of a hydration shell with the use of clusters: superoxide tetrahydrate , 2000, Science.

[27]  D. Hunting,et al.  Resonant formation of DNA strand breaks by low-energy (3 to 20 eV) electrons. , 2000, Science.

[28]  Marvin Johnson,et al.  Photoactivation of the Cl - + CH 3 Br S N 2 Reaction via Rotationally Resolved C−H Stretch Excitation of the Cl - ·CH 3 Br Entrance Channel Complex , 1999 .

[29]  Marvin Johnson,et al.  Vibrational Spectroscopy of the Ionic Hydrogen Bond: Fermi Resonances and Ion−Molecule Stretching Frequencies in the Binary X-·H2O (X = Cl, Br, I) Complexes via Argon Predissociation Spectroscopy , 1998 .

[30]  G. Gallup,et al.  ELECTRON ATTACHMENT ENERGIES OF THE DNA BASES , 1998 .

[31]  David H. Parker,et al.  Velocity map imaging of ions and electrons using electrostatic lenses: Application in photoelectron and photofragment ion imaging of molecular oxygen , 1997 .

[32]  H. Abdoul-Carime,et al.  Electron attachment to isolated nucleic acid bases , 1996 .

[33]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[34]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[35]  Mark A. Johnson,et al.  Photochemistry of hydrated electron clusters (H2O)−n (15≤n≤40) at 1064 nm: Size dependent competition between photofragmentation and photodetachment , 1988 .

[36]  W. C. Lineberger,et al.  Infrared spectrum and autodetachment dynamics of NH , 1985 .

[37]  H. Mantsch,et al.  Formate anion: The physical force field , 1981 .

[38]  Steve Scheiner,et al.  Molecular orbital investigation of multiply hydrogen bonded systems. Formic acid dimer and DNA base pairs , 1979 .

[39]  P. W. Reinhardt,et al.  Collisional ionization of Na, K, and Cs by CO2, COS, and CS2: Molecular electron affinities , 1975 .

[40]  Enrico Clementi,et al.  Study of the Electronic Structure of Molecules. XII. Hydrogen Bridges in the Guanine–Cytosine Pair and in the Dimeric Form of Formic Acid , 1971 .

[41]  Vincenzo Barone,et al.  Anharmonic vibrational properties by a fully automated second-order perturbative approach. , 2005, The Journal of chemical physics.

[42]  C. Hamilton,et al.  Stimulated Emission Pumping: New Methods in Spectroscopy and Molecular Dynamics , 1986 .