Hydrogen bond networks and electronic
properties of complex systems
Benedito José Costa Cabral
Grupo de Física Matemática
Universidade de Lisboa
1
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Parabéns Dino pelos seus extraordinários 70 anos
2
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Outline
Hydrogen bond, hydrogen bond networks, and
electronic properties
Statistical Mechanics Sampling (BOMD)
Applications
Small water clusters; liquid hydrogen cyanide
(HCN)
Conclusions
Acknowledgments
3
Hydrogen bond, hydrogen bond networks, and
electronic properties
Nature
Natureof
ofthe
theHB:
HB:complex
complexinteraction
interactiondetermined
determinedby
bycharge
charge
interactions,
interactions,dispersion
dispersioninteractions,
interactions,many-body
many-bodypolarization
polarization
effects,
effects,and
andcharge
chargetransfer.
transfer.
Hydrogen bond properties
Directionality,
Directionality,anisotropy
anisotropyor
orstrong
strongorientational
orientationalorder
order
Cooperativity:
Cooperativity:many-body
many-bodypolarization
polarizationeffects
effects
Electronic
Electronicdensity
densityreorganization:
reorganization:charge
chargetransfer
transfer
4
Directionality,
Directionality,anisotropy
anisotropyor
orstrong
strongorientational
orientationalorder
order
HCN linear chains
Cooperativity:
Cooperativity:many-body
many-bodypolarization
polarizationeffects
effects
Electronic
Electronicdensity
densityreorganization:
reorganization:charge
chargetransfer
transfer
HCN linear chains: electronic density differences
¢½n (r) =
T
½n (r)
¡
n
X
k=1
½k (r)
Hydrogen bond and HB networks
The
Themost
mostimportant
importantliquid
liquidfor
forlife
life(water)
(water)isischaracterized
characterizedby
bythe
thepresence
presence
of
a
hydrogen
bond
network
of a hydrogen bond network
Electronic
Electronicdensity
densityfluctuations
fluctuationsof
ofthe
theHB
HBnetwork
networkdetermine
determinethe
the
dynamics
dynamicsof
of(bio)chemical
(bio)chemicalprocesses
processesininwater
water
8
Hydrogen
Hydrogenbonding
bonding(in
(insmall
smallwater
waterclusters):
clusters):geometric
geometric
criterion
criterion
d[O-O] < 3.5 Angstroms; angle[OOH] < 25 Degrees
ad
a
d
ad
ad
ad
5 x ad
4 x ad
aadd
Distribution
Distributionof
ofhydrogen
hydrogenbonds
bondsin
inliquid
liquidwater
waterat
atambient
ambient
conditions
conditions
3 (aad;add) and 4 (aadd) HBs are dominant at ambient conditions
Relationship
Relationshipbetween
betweenthe
thelocal
localorganization
organizationof
ofthe
the network
network
and
andelectronic
electronicproperties
propertiesof
ofwater
water
Average monomeric dipole moment in liquid water
Average
value for
liquid water
Gas phase
Electronic polarization increases linearly with the number
of hydrogen bonds
Statistical mechanics sampling
Born-Oppenheimer molecular dynamics
12
Applications
Hydrogen
Hydrogenbond
bondnetwork
networkof
ofaa(small)
(small)water
watercluster
cluster[(H
[(H22O)
O)3232]]
Electronic
Electronicproperties
propertiesof
ofliquid
liquidhydrogen
hydrogencyanide
cyanide(HCN)
(HCN)


13
Hydrogen bond network of a (small) water cluster
Changes
Changesof
ofthe
theHB
HBnetwork
networkfrom
fromthe
theinterior
interior(bulk
(bulkwater)
water)to
tothe
the
cluster
clustersurface
surface(gas)
(gas)
Identification
Identificationof
ofaamoiety
moietyof
of“acceptor-only”
“acceptor-only”water
watermolecules
molecules
(X-ray
(X-rayexperiments)
experiments)at
atthe
thewater
watersurface.
surface.
K.R. Wilson et al JPC B (2001)
Vibrational
Vibrationalspectrum
spectrumof
ofsurface
surfacewater
waterpredicts
predictsthe
thepresence
presence
of
ofmore
morethan
than20%
20%of
ofsurface
surfacewater
watermolecules
moleculeswith
withaasingle
singleHH
atom
atomdangling
danglingaway
awayfrom
fromthe
thesurface
surface
Q. Du et al PRL (1993)
Ab
Abinitio
initioMD
MDof
ofthe
theliquid
liquidvapor-interface
vapor-interfacealso
alsopredicted
predictedthe
the
existence
existenceof
ofaasurface
surface“acceptor-only”
“acceptor-only”moiety.
moiety.
I.-F. Kuo, C.J. Mundy Science (2004)
Hydrogen bond network of a (small) water cluster
All-electron
All-electronBorn-Oppenheimer
Born-OppenheimerMolecular
MolecularDynamics
Dynamics
NVE
NVEmolecular
moleculardynamics
dynamics
DFT
DFTenergies
energiesand
andforces:
forces: Perdew-Burke-Ernzerhof
Perdew-Burke-Ernzerhof(PBE)
(PBE)
exchange-correlation
exchange-correlationfunctional
functional
55ps
psfor
forequilibration
equilibrationfollowed
followedby
by 16.5
16.5ps
psfor
forproduction;
production;
<T>=317
<T>=317±±24
24KK
N. Galamba and B.J.C. Cabral JACS (2008)
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Hydrogen bond network of a (small) water cluster
(H2 O)32
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Hydrogen bond network of a (small) water cluster
(H2 O)32
Hydrogen bond network of a (small) water cluster
dd and aa arrangements are not abundant in any region
of the cluster
da arrangements are largely dominant at the interface
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Hydrogen bond network of a (small) water cluster
Polarization effects: the average monomeric water dipole
moment in the cluster
The average monomeric dipole moment appears to be not very
dependent on geometry deformations of water molecules in the HB
network
Hydrogen bond networks and electronic properties of complex systems BJCCabral CBPF-TSALLIS2013
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
Prebiotic and extraterrestrial species closely related to
the origin of life.
C. N. Matthews, Origins of life and Evol. Biosphere (1991)
Strongly dipolar species that may form a complex HB
bond network characterized by the presence of
polymerized chains, ramified and cyclic aggregates.
I. Mamajanov, J. Herzfeld, J. Chem. Phys. (2009)
Polar domains in strongly dipolar fluids
B.J.C. Cabral, J. Chem. Phys. (2000); D.P. Shelton, J. Chem. Phys (2005)
20
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
BOMD: timestep of 0.5 fs. (NVT ) canonical ensemble at a density of
0.687 g.cm−3 and a target temperature of T=280 K (m.p T=260 K).
DFT/BOMD calculations were performed with a the Perdew-Burke21
Ernzerhof (PBE) exchange-correlation functional
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
Structure of liquid HCN
The structure of liquid HCN is mainly characterized by the presence
of linear dipole chains
22
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
Electronic polarization in liquid HCN: comparison with
the gas phase
Significant change on the average monomeric
23
dipole moment of HCN from 2.9 (G) to 3.6
D (L).
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
Electronic Absorption spectrum
Many body energy (MBE) decomposition schemes with
electrostatic embedding
E.E. Dahlke, D.G. Truhlar JCTC (2007)
M. Chiba, D.G. Fedorov, K. Kitaura JCP (2007)
R.A. Mata, H. Stoll CPL (2008)
One-body approximation (with “excitonic coupling”) to the
calculation of the first absorption band of water clusters
R.A. Mata, H. Stoll, B.J.C. Cabral JCTC (2009)
Extension to calculation of the full absorption spectra:
application to liquid HCN
H. Martiniano, B.J.C. Cabral CPL (2013)
Electronic
Electronicproperties
propertiesof
ofliquid
liquidHCN
HCN
Electronic absorption in liquid HCN
The peak position of the first absorption band (L) is blue-shifted by
0.2 eV relative to the gas-phase value.
H. Martiniano, B.J.C. Cabral CPL (2013)
25
Conclusions/Perspectives
Sequential
Sequential analysis
analysis of
of the
the electronic
electronic structure
structure of
of
configurations
configurations sampled
sampled by
by Born-Oppenheimer
Born-Oppenheimer molecular
molecular
dynamics
dynamics can
can provide
provide fundamental
fundamental information
information on
on the
the
relationship
relationshipbetween
betweenthe
thestructure
structureof
ofhydrogen
hydrogenbond
bondnetworks
networks
and
andelectronic
electronicproperties.
properties.
Coupling
Coupling of
of many-body
many-body energy
energy decomposition
decomposition schemes
schemes to
to
configurations
configurations generated
generated by
by first
first principles
principles (or
(or classical)
classical)
molecular
molecular dynamics
dynamics make
make possible
possible high
high level
level ab
ab initio
initio
calculations
calculationsof
ofthe
theelectronic
electronicproperties
propertiesin
incondensed
condensedphases
phases
Analysis
Analysis of
of the
the electronic
electronic properties
properties (and
(and dynamics)
dynamics) of
of HB
HB
networks
networksin
ininteraction
interactionwith
withcharged
chargedand
andhydrophobic
hydrophobic species
species
M.
M.Mateus,
Mateus,N.
N.Galamba,
Galamba,B.J.C.
B.J.C.Cabral,
Cabral,J.J.Chem.
Chem.Phys.
Phys.2012
2012
26
Acknowledgments
Lisboa
São Paulo
Sylvio Canuto
Kaline Coutinho
Nuno Galamba
Hugo Martiniano
Göttingen
Ricardo Mata
Fundação para a Ciência e a Tecnologia (FCT) Portugal
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