It is generally expected that the hydrogen bond strength in a D–H•••A adduct is predicted by the difference between the proton affinities (ΔPA) of D and A, measured by the adduct stabilization, and demonstrated by the infrared (IR) redshift of the D–H bond stretching vibrational frequency. These criteria do not always yield consistent predictions, as illustrated by the hydrogen bonds formed by the E and Z OH groups of protonated carboxylic acids. The ΔPA and the stabilization of a series of hydrogen bonded adducts indicate that the E OH group forms the stronger hydrogen bonds, whereas the bond length changes and the redshift favor the Z OH group, matching the results of NBO and AIM calculations. This reflects that the thermochemistry of adduct formation is not a good measure of the hydrogen bond strength in charged adducts, and that the ionic interactions in the E and Z adducts of protonated carboxylic acids are different. The OH bond length and IR redshift afford the better measure of hydrogen bond strength.
JeffreyG.A., An Introduction to hydrogen bonding, Oxford University Press, New York, USA (1997).
2.
ArnettE.M.ChawlaB.BellL.TaageperaM.HehreW.J. and TaftR.W., “Solvation and hydrogen bonding of pyridinium ions”, J. Am. Chem. Soc.99, 5729 (1977). doi: 10.1021/ja00459a034
3.
(a) DavidsonW.R.SunnerJ. and KebarleP., “Hydrogen bonding of water to onium ions. Hydration of substituted pyridinium ions and related systems”, J. Am. Chem. Soc.101, 1675 (1979); doi: 10.1021/ja00501a005 (b) LarsonJ.W. and McMahonT.B., “Formation, thermochemistry, and relative stabilities of proton-bound dimers of oxygen n-donor bases from ion cyclotron resonance solvent-exchange equilibrium measurements”, J. Am. Chem. Soc.104, 6255 (1982). doi: 10.1021/ja00387a016
4.
ShanS.LohS. and HerschlagD., “The energetics of hydrogen bonds in model systems: Implications for enzymatic catalysis”, Science272, 97 (1996). doi: 10.1126/science.272.5258.97
5.
RemerL.C. and JensenJ.H., “Toward a general theory of hydrogen bonding: The short, strong hydrogen bond [HOH…OH]−”, J. Phys. Chem. A104, 9266 (2000). doi: 10.1021/jp002726n
BianL., “Proton donor is more important than proton acceptor in hydrogen bond formation: A universal equation for calculation of hydrogen bond strength”, J. Phys. Chem. A107, 11517 (2003). doi: 10.1021/jp035446r
8.
ChanB.Del BeneJ.E. and RadomL., “Proton-bound homodimers: How are the binding energies related to proton affinities?”, J. Am. Chem. Soc.129, 12197 (2007). doi: 10.1021/ja072690d
9.
GilliP.PrettoL. and GilliG., “PA/pKa equalization and the prediction of the hydrogen-bond strength: A synergism of classical thermodynamics and structural crystallography”, J. Mol. Struct.844, 328 (2007). doi: 10.1016/j.molstruc.2007.05.014
10.
BadgerR.M. and BauerS.H., “Spectroscopic studies of the hydrogen bond. II. The shift of the O–H vibrational frequency in the formation of the hydrogen bond”, J. Chem. Phys.5, 839 (1937). doi: 10.1063/1.1749952
11.
(a) LippincottE.R. and SchroederR., “One-dimensional model of the hydrogen bond”, J. Chem. Phys.23, 1099 (1955); doi: 10.1063/1.1742196 (b) SchroederR. and LippincottE.R., “Potential function model of hydrogen bonds”, J. Phys. Chem.61, 921 (1957). doi: 10.1021/j150553a017
12.
PimentelC.G. and McClellanA.L., The hydrogen bond.Freeman, San Francisco, USA (1960).
13.
AllerhandA. and SchleyerP.v.R., “A survey of C–H groups as proton donors in hydrogen bonding”, J. Am. Chem. Soc.85, 1715 (1963). doi: 10.1021/ja00895a002
14.
BarnesA.J., “Characterization of low-barrier hydrogen bonds”, J. Mol. Struct.100, 259 (1983). doi: 10.1016/0022-2860(83)90096-0
15.
FusterF. and SilviB., “Does the topological approach characterize the hydrogen bond?”, Theor. Chem. Acc.104, 13 (2000). doi: 10.1007/s002149900100
16.
ThompsonW.H. and HynesJ.T., “Frequency shifts in the hydrogen-bonded OH stretch in halide-water clusters. The importance of charge transfer”, J. Am. Chem. Soc.122, 6278 (2000). doi: 10.1021/ja993058q
17.
AultB.S.SteinbackE. and PimentelG.C., “Matrix isolation studies of hydrogen bonding. Vibrational correlation diagram”, J. Phys. Chem.79, 615 (1975). doi: 10.1021/j100573a014
18.
Zeegers-HuyskensT., “Correlation between the frequency shift of the stretching vibration of hydrogen bond complexes and the proton affinity”, J. Mol. Liq.67, 33 (1995). doi: 10.1016/0167-7322(95)00864-0
19.
RoscioliJ.R.McCunnL.R. and JohnsonM.A., “Quantum structure of the intermolecular proton bond”, Science316, 249 (2007). doi: 10.1126/science.1138962
20.
RablenP.R.LockmanJ.W. and JorgensenW.L., “Ab Initio study of hydrogen-bonded complexes of small organic molecules with water”, J. Phys. Chem. A102, 3782 (1998). doi: 10.1021/jp980708o
21.
FrischM.J.TrucksG.W.SchlegelH.B.ScuseriaG.E.RobbM.A.CheesemanJ.R.MontgomeryJ.A.VrevenT.KudinK.N.BurantJ.C.MillamJ.M.IyengarS.S.TomasiJ.BaroneV.MennucciB.CossiM.ScalmaniG.RegaN.PeterssonG.A.NakatsujiH.HadaM.EharaM.TopyotaK.FukudaR.HasegawaJ.IshidaM.MakajimaT.HondaY.KitaoO.NakaiH.KleneM.LiX.KnowJ.E.HratchianH.P.CrossJ.B.BakkenV.AdamoC.JaramilloJ.GompertsR.StratmannR.E.YazyevO.AustlinA.J.CammiR.PomelliC.OchterskiJ.W.AyalaP.Y.MorokumaK.VothG.A.SalvadorP.DannenbergJ.J.ZakrzewskiV.G.DapprichS.DanielsA.D.StrainM.C.FarkasO.MalickD.K.RabuckA.D.RaghavachariK.ForesmanJ.B.OrtizJ.V.CuiQ.BaboulA.G.ClifforsS.CioslowskiJ.StefanovB.B.LiuG.LiashenkoA.PiskorzP.KomaromiI.MartinR.L.FoxD.J.KeithT.Al-LathamM.A.PengC.Y.NanayakkaraA.ChallacombeM.GillP.M.W.JohnsonB.ChemW.WongM.W.GanzalezC. and PopleJ.A., Gaussian 03 (Revision C.02).Gaussian, Inc., Wallingford, CT, USA (2004).
22.
(a) Del BeneJ.E.PersonW.B. and SzczepaniakK., “Properties of hydrogen-bonded complexes obtained from the B3LYP functional with 6–31G(d,p) and 6–31+G(d,p) basis sets: Comparison with MP2/6-31+G(d,p) results and experimental data”, J. Phys. Chem.99, 10705 (1995); doi: 10.1021/j100027a005 (b) PanY.P. and McAllisterM.A., “Characterization of low-barrier hydrogen bonds 4. Basis set and correlation effects: An ab initio and DFT investigation”, J. Mol. Struct.427, 221 (1998); doi: 10.1016/S0166-1280(97)00227-3 (c) KonéM.IllienB.GratonJ. and LaurenceC., “B3LYP and MP2 calculations of the enthalpies of hydrogen-bonded complexes of methanol with neutral bases and anions: Comparison with experimental data”, J. Phys. Chem. A109, 11907 (2005). doi: 10.1021/jp054173s
23.
(a) CurtissL.A.RaghavachariK.RedfernP.C.RassolovV. and PopleJ.A., “Gaussian-3 (G3) theory for molecules containing first and second-row atoms”, J. Chem. Phys.109, 7764 (1998); doi: 10.1063/1.477422 (b) BaboulA.G.CurtissL.A.RedfernP.C. and RaghavachariK., “Gaussian-3 theory using density functional geometries and zero-point energies”, J. Chem. Phys.110, 7650 (1999); doi: 10.1063/1.478676 (c) CurtissL.A.RedfernP.C.RassolovV.KedzioraG. and PopleJ.A., “Extension of Gaussian-3 theory to molecules containing third-row atoms K, Ca, Ga, Kr”, J. Chem. Phys.114, 9287 (2001). doi: 10.1063/1.1366337
24.
NicolaidesA.RaukA.GlukhovtsevM.N. and RadomL., “Heats of formation from G2, G2(MP2), and G2(MP2,SVP) total energies”, J. Phys. Chem.100, 17460 (1996). doi: 10.1021/jp9613753
(a) XantheasS.S., “On the importance of the fragment relaxation energy terms in the estimation of the basis set superposition error correction to the intermolecular interaction energy”, J. Chem. Phys.104, 8821 (1996); doi: 10.1063/1.471605 (b) BowenJ.P.SorensenJ.B. and KirschnerK.N., “Calculating interaction energies using first principle theories: Consideration of basis set superposition error and fragment relaxation”, J. Chem. Ed.84, 1225 (2007).
27.
(a) GrabowskiS.J. and SokalskiA.W., “Different types of hydrogen bonds: Correlation analysis of interaction energy components”, J. Phys. Org. Chem.18, 779 (2005); doi: 10.1002/poc.937 (b) GrabowskiS.J., “Theoretical studies of hydrogen bonding”, Ann. Rep. Progr. Chem., Sect C102, 131 (2006).
28.
(a) BoysS.F. and BernardiF., Mol. Phys.19, 553 (1970); doi: 10.1080/00268977000101561 (b) van DuijneveldtF.B.van Duijneveldt-Van de RijdtJ.G.C.M. and van LentheJ.H., “State of the art in counterpoise theory”, Chem. Rev.; 94, 1873 (1994); doi: 10.1021/cr00031a007 (c) JensenF., Introduction to computational chemistry.John Wiley & Sons Ltd, Chichester, UK (1999).
29.
(a) MasamuraM., “The effect of basis set superposition error on the convergence of interaction energies”, Theor. Chem. Acc.106, 301 (2001); doi: 10.1007/s002140100280 (b) CramerC.J., Essentials of computational chemistry, John Wiley & Sons Ltd, Chichester, UK (2002).
30.
BaderR.A.W., Atoms in molecules.Clarendon Press, Oxford, UK (1990).
31.
KochU. and PopelierP.L.A., “Characterization of C–H–O hydrogen bonds on the basis of the charge density”, J. Phys. Chem.99, 9747 (1995). doi: 10.1021/j100024a016
32.
ReedA.E.CurtissL.A. and WeinholdF., “Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint”, Chem. Rev.88, 899 (1988). doi: 10.1021/cr00088a005
33.
SchaftenaarG. and NoordikJ.H., “Molden: A pre-and post-processing program for molecular and electronic structures”, J. Comput.-Aided Mol. Design14, 123 (2000). doi: 10.1023/A:1008193805436
34.
Xaim; A program developed by AlbaOrtiz J.C. and JanéC.B., Universitat Rovirai Virgili, Tarragona, Spain; http://www.quimica.urv.es/XAIM/.
35.
HillenbrandE.A. and ScheinerS., “Analysis of the principles governing proton-transfer reactions. Carboxyl group”, J. Am. Chem. Soc.108, 7178 (1986). doi: 10.1021/ja00283a007
36.
(a) HockingW.H., “Other rotamer of formic acid, cis-HCOOH, Z. Naturforsch. A31, 1113 (1976); (b) BjarnovE. and HockingW.H., “Structure of other rotamer of formic acid, cis-HCOOH, Z. Naturforsch. A33, 610 (1978).
37.
(a) CarrollT.X.SmithS.R. and ThomasT.D., “Correlation between proton affinity and core-electron ionization potentials for double-bonded oxygen. Site of protonation in esters”, J. Am. Chem. Soc.97, 659 (1975); doi: 10.1021/ja00836a042 (b) BenoitF.M. and HarrisonA.G., “Predictive value of proton affinity. Ionization energy correlations involving oxygenated molecules”, J. Am. Chem. Soc.99, 3980 (1977). doi: 10.1021/ja00454a015
38.
PattenK.O. and AndrewsL., “Fourier-transform infrared spectra of hydrogen fluoride complexes with acetic acid and methyl acetate in solid argon”, J. Phys. Chem.90, 1073 (1986). doi: 10.1021/j100278a023
39.
GörbitzC.H. and EtterM.C., “Hydrogen bonds to carboxylate groups. Syn/anti distributions and steric effects”, J. Am. Chem. Soc.114, 627 (1992). doi: 10.1021/ja00028a031
40.
MiddlemissN.E. and HarrisonA.G., “Structure and fragmentation of protonated carboxylic acids in the gas-phase”, Can. J. Chem.57, 2827 (1979). doi: 10.1139/v79-459
41.
FusterF.SilviB.BerskiS. and LatajkaZ., “Topological aspects of protonation and hydrogen bonding: The dihydrogen bond case”, J. Mol. Struct.555, 75 (2000). doi: 10.1016/S0022-2860(00)00589-5
42.
SteinerT., “The hydrogen bond in the solid state”, Angew. Chem. Int. Ed.41, 48 (2002). doi: 10.1002/1521-3773(20020104)41:1<48::AID-ANIE48>3.0.CO;2-U
43.
BarrosoM.ArnaultL.G. and FormosinhoS.J., “Absolute rate calculations: Atom and proton transfers in hydrogen-bonded systems”, ChemPhysChem.6, 363 (2005). doi: 10.1002/cphc.200400285
44.
TaoL.HanJ. and TaoF.-M., “Correlations and predictions of carboxylic acid pKa values using intermolecular structure and properties of hydrogen-bonded complexes”, J. Phys. Chem. A112, 775 (2008); doi: 10.1021/jp710291c; for an early experimental precedent, see GordyW. and StanfordS.C., “Spectroscopic evidence for hydrogen bonds: Comparison of proton-attracting properties of liquids”, J. Chem. Phys.8, 170 (1940) 10.1063/1.1750625 and HammettL.P., “The determination of the proton-attracting properties of liquids”, J. Chem. Phys.8, 644 (1940). doi: 10.1063/1.1750734
45.
ChanB.Del BeneJ.E.ElgueroJ. and RadomL., “On the relationship between the preferred site of hydrogen bonding and protonation”, J. Phys. Chem. A109, 5509 (2005). doi: 10.1021/jp0516994
(a) FridgenT.D., “Structures of heterogeneous proton-bond dimers with a high dipole moment monomer: Covalent vs electrostatic interactions, J. Phys. Chem. A110, 6122 (2006); doi: 10.1021/jp057335t (b) BurtM.B. and FridgenT.D., “Heterogeneous proton-bound dimers with a high dipole moment monomer: How could we experimentally observe these anomalous ionic hydrogen bonds?”, J. Phys. Chem. A111, 10738 (2007). doi: 10.1021/jp075086y
48.
(a) BoumaW.J. and RadomL., “Is the carboxylic acid fluoride bond really the strongest type of hydrogen bond?”, Chem. Phys. Lett.64, 216 (1979); doi: 10.1016/0009-2614(79)80499-6 (b) ProssA. and RadomL., “Effect of substituents on the structure of reaction complexes”, J. Am. Chem. Soc.103, 6049 (1981). doi: 10.1021/ja00410a010
49.
(a) MóO.YáñezM. and ElgueroJ., “Cooperative (nonpairwise) effects in water trimers—an ab initio molecular orbital study”, J. Chem. Phys.97, 6628 (1992); doi: 10.1063/1.463666 (b) EspinosaE.SouhassouM.LachekarH. and LecomteC., “Topological analysis of the electron density in hydrogen bonds, Acta Cryst.B55, 563 (1999); doi: 10.1107/S0108768199002128 (c) GrabowskiS.J., “Properties of a ring critical point as measures of intramolecular H-bond strength”, Monatsh. Chem.133, 1373 (2002). doi: 10.1007/s00706-002-0498-3
50.
MagnoliD.E. and MurdochJ.R., “Kinetic and thermodynamic contributions to energy barriers and energy wells: Application to proton-bound dimers in gas-phase proton-transfer reactions”, J. Am. Chem. Soc.103, 7465 (1981). doi: 10.1021/ja00415a011
51.
(a) ScheinerS. and RedfernP., “Quantum mechanical test of Marcus theory. Effects of alkylation upon proton transfer, J. Phys. Chem.90, 2969 (1986); doi: 10.1021/j100404a036 (b) ScheinerS., Hydrogen bonding, a theoretical perspective, Oxford University Press, NewYork, USA (1997).
52.
(a) HumbelS.HoffmannN.CôteI. and BouquartJ., “Substituent effects on two-center three-electron bonds and hydrogen bonds involving unsaturated organic functional groups and an ammonia radical cation—The resonance contribution”, Chem. Eur. J.6, 1592 (2000); doi: 10.1002/(SICI)1521-3765(20000502)6:9<1592::AID-CHEM1592>3.3.CO;2-N (b) HumbelS., “Short strong hydrogen bonds: A valence bond analysis”, J. Phys. Chem. A106, 5517 (2002). doi: 10.1021/jp0202789
53.
UmeyamaH. and MorokumaK., “The origin of hydrogen bonding. An energy decomposition study”, J. Am. Chem. Soc.99, 1316 (1977). doi: 10.1021/ja00447a007
54.
(a) GlendeningE.D. and StreitwieserA., “Natural energy decomposition analysis: An energy partitioning procedure for molecular interactions with application to weak hydrogen bonding, strong ionic, and moderate donor-acceptor interactions”, J. Chem. Phys.100, 2900 (1994); doi: 10.1063/1.466432 (b) PendásA.M.BlancoM.A. and FranciscoE., “The nature of the hydrogen bond: A synthesis from the interacting quantum atoms picture”, J. Chem. Phys.125, 184112 (2006). doi: 10.1063/1.2378807
55.
GrantD.J.MatusM.H.SwitzerJ.R.DixonD.A.FranciscoJ.S. and ChristeK.O., “Bond dissociation energies in second-row compounds”, J. Phys. Chem. A112, 3145 (2008). doi: 10.1021/jp710373e
56.
(a) BadgerR.M., “A relation between internuclear distances and bond force constants”, J. Chem. Phys.2, 128 (1934); doi: 10.1063/1.1749433 (b) BadgerR.M., “The relation between the internuclear distances and force constants of molecules and its application to polyatomic molecules”, J. Chem. Phys.3, 710 (1935). doi: 10.1063/1.1749581
57.
(a) HilbertG.E.WulfO.R.HendricksS.B. and LiddelU., “The hydrogen bond between oxygen atoms in some organic compounds”, J. Am. Chem. Soc.58, 548 (1936); doi: 10.1021/ja01295a002 (b) HendricksS.B.WolfO.R.HilbertG.E. and LiddelU., “Hydrogen bond formation between hydroxyl groups and nitrogen atoms in some organic compounds”, J. Am. Chem. Soc.58, 1991 (1936). doi: 10.1021/ja01301a050
