The%20Hydrogen%20Bond

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The Hydrogen Bond
Jan LundellDepartment of Chemistry, University
of Jyväskylä
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The Hydrogen Bond
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The Hydrogen Bond
Peter Agre (Nobel Prize, 2003) The purest form
of hydrogen bond there is
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The Hydrogen Bond

• The hydrogen nucleus held by two octets
  constitutes a weak bond
• W.M.Latimer and W.H.Rodebush, JACS 42, 1920,
  1419
• Under certain conditions an atom of hydrogen is
  attracted by rather strong forces to two atoms
  instead of only one, so that it may be considered
  to be acting as a bond between them. This is
  called a hydrogen bond.
• L. Pauling, Nature of Chemical Bond, 1939

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The Hydrogen Bond
HCOOH in the gas phase IR ( from
webbook.nist.gov )
Absorbance
Wavenumber
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The Hydrogen Bond

• A hydrogen bond exists between the functional
  group, A-H, and an atom or a group of atoms, B,
  in the same or different molecules when
• (a) there is evidence of bond formation
  (association or chelation)
• (b) there is evidence that this new bond linking
  A-H and B specifically involves a hydrogen atom
  already bonded to A
• G.C.Pimentel, A.L.McClellan, The Hydrogen Bond,
  1960

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The Hydrogen Bond
Strong
Medium
Weak
bond distance A-H ? H...B A-H lt H...B A-H ltlt H...B
H...B (Å) ?1.2 - 1.5 ?1.5 - 2.2 2.2 - 3.2
A...B (Å) 2.2 - 2.5 2.5 - 3.2 3.2 - 4.0
bond angle (º) 175 - 180 130 - 180 90 - 150
binding energy (kJ/mol) 60 - 170 15 - 60 lt 15
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The Hydrogen Bond
Strong
Medium
Weak
dimers of strong acids and bases in the gas phase acids dimers of weak acids and bases in the gas phase
Acid salts alcohols, phenols C-H...O/N
Proton sponges hydrates O/N-H...?
HF complexes all biological molecules dihydrogen bonds
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The Hydrogen Bond

• A hydrogen atom with only one stable orbital
  cannot form more than one pure covalent bond and
  the attraction of the two atoms observed in
  hydrogen bond formation must be due largely to
  ionic forces
• L.Pauling, The Nature of Chemical Bond, 1939

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The Hydrogen Bond

• YHB aYa bYb cYc dYd eYe
• Ya A-HB covalent A-H bond
• Yb A- -H B ionic A-H bond
• Yc A- -HB charge transfer , AB bond
• Yd A -H- B ionic A-H bond
• Ya A-H- B charge transfer, HB bond
• C.A.Coulson, In Hydrogen Bonding, D.Hadzi
  (Ed.) 1959, pp. 339-360.

O-H O with O O 2.8 Å Yb Yd
contribute 65 of the hydrogen bond energy
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Interaction energy of a H-bond

• Supermolecular approach
• Eint EAB (EA EB)

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Interaction energy decomposition scheme
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HCNHCN ( MP2 )
A.Heikkilä, J.Lundell, J.Phys.Chem. A 104, 2000,
6637-6643
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Symmetry-Adapted Perturbation Theory (SAPT)
K.Szalewicz, K.Patkowski, B.Jeziorski
,Struct.Chem. 116, 2005, 43-117
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R.A.Christie, K.D.Jordan, Struct.Chem. 116, 2005,
27-41
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Having more than two molecules?
S.S.Xantheas Struct.Chem. 116, 2005, 119-148
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S.S.Xantheas Struct.Chem. 116, 2005, 119-148
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Non-additive (cooperative) effects
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S.S.Xantheas Struct.Chem. 116, 2005, 119-148
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Basis set superposition error (BSSE)

• Not perfect basis sets, so needs to borrow from
  the neighbour

HNCHCN
The cure Counterpoise correction
(Boys-Bernardi )
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S.S.Xantheas Struct.Chem. 116, 2005, 119-148
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J.R.Lane, H.G.Kjaergaard, J.Phys.Chem. 131, 2009,
034307
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Changes upon hydrogen bonding
G.A.Jeffrey, An Introduction to Hydrogen Bonding,
1997
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HCOOH photochemistry in matrices
H2O CO vs CO2 H2
J.Lundell, M.Räsänen, J.Phys.Chem. 99, 1995,
14301.
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H2O...CO Two stable complex structures
J.Lundell, J.Phys.Chem. 99, 1995,14290J.Lundell,
Z.Latajka, J.Phys.Chem. A 101, 1997, 5004
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H2O...CO Experiments

• In situ photolysis of formic acid in a solid
  argon matrix

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H2O...CO Experiments

• Annealing the matrix after photolysis

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H2O...CO Experiments

• Both HOH...CO and HOH...OC can be made

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Can we do more?
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Anharmonic calculations cc-VSCF

• Vibrational Schrödinger equation in mass-weighted
  normal mode coordinates
• single-mode wavefunctions, energies and
  effective potentials
• 2nd order perturbation theory for correlation
  effects between different vibrational modes
• pairwise interactions between normal modes

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Anharmonic calculations cc-VSCF

• Grid-approach of PES
• - 8 ? 8 or 16 ? 16 grids
• - points chosen equidistantly over an interval
  defined by the harmonic frequency of a
  vibrational modeQmax inverse square root of
  the frequencyG.M.Chaban, J.O.Jung, R.B.Gerber,
  J.Phys.Chem. A 104, 2000, 2772
• Implemented in GAMESS-US

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MP2/aug-cc-pVTZ cc-VSCF
CO2...H2
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MP2/aug-cc-pVTZ cc-VSCF
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The formic acid monomer Two conformers
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IR-pumping at 6934 cm-1 (2 nOH)
M.Pettersson, J.Lundell, L.Khriachtchev,
M.Räsänen, JACS 119, 1997, 11715
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HCOOH anharmonic calculations
trans-HCOOH
anharmonic
harmonic
cis-HCOOH
E.M.S.Macoas, J.Lundell, M. Pettersson,
L.Khriachtchev, R.Fausto, M.Räsänen,
J.Mol.Spectrosc. 219, 2003, 70.
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Isomerisation of formic acid The monomer
trans
cis
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The trans-trans formic acid dimers
MP2/6-311G(2d,2p)
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The trans-trans dimer (FAD-tt1)
FAD-tt1 in solid argon
From M.Gantenberg, M.Halupka, W.Sander,
Chem.Eur.J. 6, 2000, 1865
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Solid argon
A.Olbert-Majkut, J.Ahokas, J.Lundell,
M.Pettersson, Chem.Phys.Lett. 468, 2009, 176.
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The trans-trans formic acid dimers
FAD-tt3 FAD-tt6
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Pumping O-H str in trans-trans dimer ?




K.Marushkevich, L.Khriachtchev, J.Lundell,
M.Räsänen, JACS 128, 2006, 12060
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The cis-trans formic acid dimers
MP2/6-311G(2d,2p)
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The cis-trans formic acid dimers
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The cis-trans formic acid dimers
MP2/6-311G(2d,2p)
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Photoisomerisation of formic acid dimers
Computed relative energies
FAD-tc4
FAD-cc1
FAD-cc5
FAD-tc5
FAD-tt3
FAD-tc3
FAD-tt6
FAD-tc2
FAD-tt5
FAD-tc1
FAD-tt4
FAD-tt2
cis-FA
Experimentally observed
FAD-tt1
trans-FA
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The cis-cis formic acid dimers
MP2/6-311G(2d,2p)
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The cis-cis formic acid dimers
?
?
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Current topics(Horizons in Hydrogen Bond
Research, Paris, Sept 2009)

• Blue-shifting hydrogen bonds vs red-shifting
  hydrogen bonds
• Dihydrogen bonds (for example, H-O-HHXeH )
• Biomolecular systems
• - Water as biolubricant
• Fast spectroscopy (also dynamic simulations )