The proton affinity of water dimer was measured, using the kinetic method with nitrile reference bases, to be 808±6 kJ mol−1. The difference between the measured value and the proton affinity of a single water molecule (690±4 kJ mol−1) reflects the difference in solvation energy for two neutral water molecules (the hydrogen bond energy of water dimer), and the energy for solvation of hydronium cation and water. Using the measured proton affinity of the dimer along with ancillary data yields an experimental value of the hydrogen bond energy of neutral water dimer, 18±9 kJ mol−1, in good agreement with previous experimental and theoretical values. The proton affinity of the dimer measured by using alcohol references is ca 100 kJ mol−1 too low, likely because the structure of the protonated cluster is not well-suited for kinetic method measurements. These results highlight the importance of choosing reference bases that form cluster ions consisting of a proton bound complex between the water dimer and the reference base.
HugginsM.L., “50 Years of Hydrogen Bond Theory”, Angew. Chemie Int. Ed. English10, 147 (1971).
2.
GrabowskiS.J., “Hydrogen Bonding Strength-Measures Based on Geometric and Topological Parameters”, J. Phys. Org. Chem.17, 18 (2004).
3.
KollmanP.A.AllenL.C., “The Theory of the Hydrogen Bond”, Chem. Rev.72, 283 (1972).
4.
KeutschF.N.SaykallyR.J., “Water Clusters: Untangling the Mysteries of the Liquid, One Molecule at a Time”, Proc. Nat. Acad. Sci.98, 10533 (2001).
5.
GoldmanN.FellersR.S.LeforestierC.SaykallyR.J., “Water Dimers in the Atmosphere: Equilibrium Constant for Water Dimerization from the VRT(ASP-W) Potential Surface”, J. Phys. Chem. A105, 515 (2001).
RowlinsonJ.S., “The Lattice Energy of Ice and the Second Virial Coefficient of Water Vapour”, Trans. Faraday Soc.47, 120 (1951).
8.
KellG.S.McLaurinG.E.WhalleyE., “PVT Properties of Water. II. Virial Coefficients in the Range 1500-4500C Without Independent Measurement of Vapor Volumes”, J. Chem. Phys.48, 3805 (1968).
9.
BohlanderR.A.GebbieH.A., “Molecular Complexity of Water Vapour and the Speed of Sound”, Nature253, 523 (1975).
10.
McCulloughJ.P.PenningtonR.E.WaddingtonG., “A Calorimetric Determination of the Vapor Heat Capacity of Gas Imperfection of Water”, J. Am. Chem. Soc.74, 4439 (1952).
11.
CurtissL.A.FruripD.J.BlanderM., “Studies of Molecular Association in H2O and D2O Vapors by Measurement of Thermal Conductivity”, J. Chem. Phys.71, 2703 (1979).
12.
GebbieH.A.BurroughsW.J.ChamberlainJ.HarriesJ.E.JonesR.G., “Dimers of the Water Molecule in the Earth's Atmosphere”, Nature221, 143 (1969).
13.
FellersR.S.LeforestierC.BralyL.B.BrownM.G.SaykallyR.J., “Spectroscopic Determination of the Water Pair Potential”, Science284, 945 (1999).
14.
GoldmanN.FellersR.S.BrownM.G.BralyL.B.KeoshianC.J.LeforestierC.SaykallyR.J., “Spectroscopic Determination of the Water Dimer Intermolecular Potential-Energy Surface”, J. Chem. Phys.116, 10148 (2002).
15.
LeforestierC.GattiF.FellersR.S.SaykallyR.J., “Determination of a Flexible (12D) Water Dimer Potential via Direct Inversion of Spectroscopic Data”, J. Chem. Phys.117, 8710 (2002).
16.
BurnhamC.J.XantheasS.S., “Development of Transferable Interaction Models for Water. I. Prominent Features of the Water Dimer Potential Energy Surface”, J. Chem. Phys.116, 1479 (2002).
17.
MorokumaK.PedersenL., “Molecular-Orbital Studies of Hydrogen Bonds. An Ab Initio Calculation for Dimeric H2O”, J. Chem. Phys.48, 3275 (1968).
18.
BolanderR.W.KassnerJ.L.JrZungJ.T., “Semiempirical Determination of the Hydrogen Bond Energy for Water Clusters in the Vapor Phase. I. General Theory and Application to the Dimer”, J. Chem. Phys.50, 4402 (1969).
19.
KollmanP.A.AllenL.C., “Theory of the Hydrogen Bond: Electronic Structure and Properties of the Water Dimer”, J. Chem. Phys.51, 3286 (1969).
20.
BowersM.J.T.PitzerR.M., “Bond Orbital Analysis of the Hydrogen Bond in the Linear Water Dimer”, J. Chem. Phys.59, 163 (1973).
21.
FeyereisenM.W.FellerD.DixonD.A., “Hydrogen Bond Energy of the Water Dimer”, J. Phys. Chem.100, 2993 (1996).
22.
TschumperG.S.LeiningerM.L.HoffmanB.C.ValeevE.F.SchaeferH.F.IIIQuackM., “Anchoring the Water Dimer Potential Energy Surface with Explicitly Correlated Computations and Focal Point Analysis”, J. Chem. Phys.116, 690 (2002).
23.
JursicB.S., “Study of the Water-Methanol Dimer with Gaussian and Complete Bases Set ab Initio, and Density Functional Theory Methods”, Theochem466, 203 (1999).
24.
BakoI.PalinkasG., “Ab Initio Studies of Methanol, Methanethiol and Methylamine Dimer”, Theochem594, 179 (2002).
25.
MoO.YanezM.ElgueroJ., “Study of the Methanol Trimer Potential Energy Surface”, J. Chem. Phys.107, 3592 (1997).
26.
KieningerM.SuhaiS., “Density Function Studies on Hydrogen-Bonded Complexes”, Int. J. Quantum Chem.52, 465 (1994).
27.
SimonS.DuranM.DannenbergJ.J., “Effect of Basis Set Superposition Error on the Water Dimer Surface Calculated at Hartree-Fock, Moller-Plesset, and Density Functional Theory Levels”, J. Phys. Chem. A103, 1640 (1999).
28.
HuangN.MacKerellA.D.Jr, “An ab Initio Quantum Mechanical Study of Hydrogen-Bonded Complexes of Biological Interest”, J. Phys. Chem. A106, 7820 (2002).
PaciosL.F., “Topological Descriptors of the Electron Density and the Electron Localization Function in Hydrogen Bond Dimers at Short Intermonomer Distances”, J. Phys. Chem. A108, 1177 (2004).
31.
CooksR.G.WongP.S.H., “Kinetic Method of Making Thermochemical Determinations: Advances and Applications”, Acc. Chem. Res.31, 379 (1998).
32.
CooksR.G.KoskinenJ.T.ThomasP.D., “The Kinetic Method of Making Thermochemical Determinations”, J. Mass Spectrom.34, 85 (1999).
33.
McLuckeyS.A.CameronD.CooksR.G., “Proton Affinities from Dissociations of Proton-Bound Dimers”, J. Am. Chem. Soc.103, 1313 (1981).
34.
ArmentroutP.B., “Entropy Measurements and the Kinetic Method: A Statistically Meaningful Approach”, J. Am. Soc. Mass Spectrom.11, 371 (2000).
35.
HokeS.H.IIYangS.S.CooksR.G.HrovatD.A.BordenW.T., “Proton Affinities of Free Radicals Measured by the Kinetic Method”, J. Am. Chem. Soc.116, 4888 (1994).
36.
ClevenC.D.HokeS.H.IICooksR.G.HrovatD.A.SmithJ.M.LeeM.S.BordenW.T., “Effect of Olefin Pyramidalization on the Proton Affinity of Tricyclo[3.3.3.03,7]undec-3(7)-ene as Determined by ab Initio Calculations and Kinetic Method Measurements”, J. Am. Chem. Soc.118, 10872 (1996).
37.
WentholdP.G.SquiresR.R., “Gas-Phase Acidities of o-, m-, and p-dehydrobenzoic Acid Radicals. Determination of the Substituent Constants for a Phenyl Radical Site”, Int. J. Mass Spectrom. Ion Processes175, 215 (1998).
38.
GraulS.T.SchnuteM.E.SquiresR.R., “Gas-Phase Acidities of Carboxylic Acids and Alcohols From Collision-Induced Dissociation of Dimer Cluster Ions”, Int. J. Mass Spectrom. Ion Processes96, 181 (1990).
39.
MarinelliP.J.PaulinoJ.A.SunderlinL.S.WentholdP.G.PoutsmaJ.C.SquiresR.R., “A Tandem Selected Ion Flow Tube-Triple Quadrupole Instrument”, Int. J. Mass Spectrom. Ion Processes130, 89 (1994).
40.
CaoJ.HolmesJ.L., “The Determination of Proton Affinities of Secondary Alcohols from the Dissociation of Proton-Bound Molecular Trios. A New Application of the Kinetic Method”, Eur. J. Mass Spectrom.7, 243 (2001).
41.
MaS.WongP.YangS.S.CooksR.G., “Gas-Phase Molecular, Molecular Pair, and Molecular Triplet Fe+ Affinities of Pyridines”, J. Am. Chem. Soc.118, 6010 (1996).
42.
ErvinK.M., “Microcanonical Analysis of the Kinetic Method. The Meaning of the ‘Effective Temperature’”, Int. J. Mass Spectrom.195/196, 271 (2000).
43.
DrahosL.VekeyK., “How Closely Related are the Effective and the Real Temperature”, J. Mass Spectrom.34, 79 (1999).
44.
ErvinK.M., “Microcanonical Analysis of the Kinetic Method. The Meaning of the “Apparent Entropy”, J. Am. Soc. Mass Sepctrom.13, 435 (2002).
45.
CaoJ.AubryC.HolmesJ.L., “Proton Affinities of Simple Amines: Entropies and Enthalpies of Activation and Their Effect on the Kinetic Method for Evaluating Proton Affinities”, J. Phys. Chem. A104, 10045 (2000).
46.
HolmesJ.L.AubryC.MayerP.M., “Proton Affinities of Primary Alkanols: An Appraisal of the Kinetic Method”, J. Phys. Chem. A103, 705 (1999).
47.
CerdaB.A.WesdemiotisC., “Li+, Na+, and K+ Binding to the DNA and RNA Nucleobases. Bond Energies and Attachment Sites from the Dissociation of Metal Ion-Bound Heterodimers”, J. Am. Chem. Soc.118, 11884 (1996).
48.
CerdaB.A.HoyauS.OhanessianG.WesdemiotisC., “Na+ Binding to Cyclic and Linear Dipeptides. Bond Energies, Entropies of Na+ Complexation, and Attachment Sites from the Dissociation of Na+-Bound Heterodimers and ab Initio Calculations”, J. Am. Chem. Soc.120, 2437 (1998).
49.
CerdaB.A.WesdemiotisC., “Gas Phase Copper(I) Ion Affinities of Valine, Lysine, and Arginine Based on the Dissociation of Cu+-Bound Heterodimers at Varying Internal Energies”, Int. J. Mass Spectrom.185–187, 107 (1999).
50.
ChengX.WuZ.FenselauC., “Collision Energy Dependence of Proton-Bound Dimer Dissociation: Entropy Effects, Proton Affinities, and Intramolecular Hydrogen-Bonding in Protonated Peptides”, J. Am. Chem. Soc.115, 4844 (1993).
51.
BouchouxG.DjaziF.GaillardF.VierezetD., “Application of the Kinetic Method to Bifunctional Bases MIKE and CID-MIKE Test Cases”, Int. J. Mass Spectrom.227, 479 (2003).
52.
WentholdP.G., “Determination of the Proton Affinities of Bromo- and Iodoacetonitrile Using the Kinetic Method With Full Entropy Analysis”, J. Am. Soc. Mass Spectrom.11, 601 (2000).
53.
HunterE.P.LiasS.G., “Proton Affinity Evaluation”, in NIST Chemistry Webbook, Ed by LinstromP.J.MallardW.G., National Institutes of Standards and Technology, Gaithersburg, MD 20899, USA (March 2003) (http://webbook.nist.gov).
54.
Meot-NerM.M.LiasS.G., “Binding Energies Between Ions and Molecules and The Thermochemistry of Cluster Ions”, in NIST Chemistry Webbook, Ed by LinstromP.J.MallardW.G., National Institutes of Standards and Technology, Gaithersburg, MD 20899, USA (March 2003) (http://webbook.nist.gov).
55.
Moet-Ner (Mautner)M., “The Proton Affinity Scale, and Effects of Ion Structure and Solvation”, Int. J. Mass Spectrom.227, 525 (2003).
56.
SzulejkoJ.E.McMahonT.B., “Progress Toward an Absolute Gas-Phase Proton Affinity Scale”, J. Am. Chem. Soc.115, 7839 (1993).
57.
DalleskaN.F.HonmaK.ArmentroutP.B., “Stepwise Solvation Enthalpies of Protonated Water Clusters: Collision-Induced Dissociation as an Alternative to Equilibrium Studies”, J. Am. Chem. Soc.115, 12125 (1993).
58.
BuckinghamA.D., “The Hydrogen Bond, and the Structure and Properties of H2O and (H2O)2”, J. Mol. Struct.250, 111 (1991).
59.
GraulS.T.SquiresR.R., “Energy-Resolved Collision-Induced Dissociation of Proton-Bound Cluster Ions as a Structural Probe: The Acetonitrile-Water System”, Int. J. Mass Spectrom. Ion Processes94, 41 (1989).
