potential energy surfaces fernando pirani dipartimento di chimica universita’ degli studi di...
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Potential energy surfaces
Fernando PiraniDipartimento di Chimica
Universita’ degli studi di Perugia
Erice 1-7 Agosto 2005
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The detailed knowledge of theInteraction V(R) is still a challenge
Presented topics:• well assessed arguments• questions under investigation• future perspectives
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The detailed characterization and modelling of the intermolecular interaction requires the combination of
New experiments
Extensive ab initio calculations
Development of empirical and semiempiricalmethods
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Absorption spectroscopy
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Differential cross section
diffraction oscillations
rainbow
scattering angle
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Integralcross section
the Lambert Beer law
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glory oscillations
average value ~v-2/5
collision velocity , v
Inte
gral
cro
ss s
ectio
n, Q
(v)
Inte
ract
ion
pote
ntia
l , V
intermolecular distance, R
diffraction oscillations
rainbow
diffe
rent
ial c
ross
sec
tion
scattering angle
Scattering investigations
glory
diffractions rainbow
Q(v
)v2
/5
v
average value
average value
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Perugia experimentalsetup for integral crosssection measurements
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Experimental Apparatus
cell
I0
N
S
I0 IB
I
IB / I0Beam transmittance (paramagnetism)
I / I0Beam attenuation (intermolecular forces)
scatteringchamber
entrance slitto the detector
ionizer
quadrupolemass filter
electronmultiplier
beam defining slit
60cm 32cm
supersonicbeam source
velocityselector
skimmers
cryostat
50cm 12cm 38cm
Stern-Gerlachmagnet
chopper
velocity selection
magnetic analysis
scattering experiments
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V(R)
R
π
0
dsin ),(2
1RVV
(O2)=1.60 Å3
(Ar)=1.64 Å3
If the molecule rotate faster then thetime required for a collision, an effectiveaveraged interaction drives the collision
Ar-Kr
O2-Kr
(b) 10 K
(a) 1000 K
F.Pirani et al. JCP 75, 1042 (1981)
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O2-Kr
The scattering of aligned molecules: the anisotropy in van der Waals interactions
V. Aquilanti et al., JCP, 109, 3898 (1998)
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The glory shift: a signature of an embryonic H-bond
V. Aquilanti et al., Angew. Chem. Int. Ed., 117, 2408 (2005)
αH2O=1.47 Ǻ3
αO2=1.60 Ǻ3
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The glory shift and quenching: the role of additional components to vdW
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The glory quenching and its modification with the controlled change in the sublevels of the Cl atoms provide information on the spherical component V0 (vdW) and on the interaction anisotropy V2
V2 – configuration
interaction
Kr+Cl-
Kr Cl
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Ab initio methods
Supermolecule Approach
VAB = EAB - EA - EBwhere EAB denotes the energy of the supermolecule andEA and EB the partners energies
Perturbation Theory
VAB = Vex.rep.+ Vch.tr.+ Vind+ Vdisp+ Velectr + …
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Semiempirical and empirical methods
• Identification of the leading interaction components
VAB = Vex.rep.+ Vind+ Vdisp + Vch.tr.+ Velectr = VvdW + Vch.tr.+ Velectr
Semiempirical:representation of each component by theoretical formulas where some quantities are identified with basic properties of involved partners
Empirical:representation of each component by empirical formulas given in terms of fundamental physical properties of involved partners (polariz., charge, permanent multipole, ioniz. potential, electron affinity…)
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The polarizability properly scales both attraction and repulsion
Further applications:
ion–neutral Chem.Phys.Lett. 183, 297 (1991)multicharged ion–neutral and ion–ion Chem.Phys. 209, 299 (1996)Atom (ion)-polyatomic molecule – Chem.Phys.Lett 350, 286 (2001); Chem.Phys.Lett. 394, 37 (2004)
When only van der Waals forces are operative!
Neutral-neutral J. Chem. Phys., 95, 1852 (1991)
attraction ~ R-6 (n-n) || ~ R-4 (i-n)
repulsion
well region
pote
nti
al en
erg
y
intermolecular distance
1/3
mole
cu
lar
volu
me
molecular polarizabilityatomic radius
εRm
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Models for the representation of intermolecular forces
095.0
3/13/1
767.1attraction
repulsion
BA
BAmR
2/12/16 7.15
B
B
A
A
BA
NN
C
6672.0mR
C
Other references:ion–neutral Chem.Phys.Lett. 183, 297 (1991)multicharged ion–neutral and ion–ion Chem.Phys. 209, 299 (1996)atom-polyatomic molecule – Chem.Phys.Lett. 350, 286 (2001)Chem.Phys.Lett. 397, 37 (2004)
van der Waals forces
J. Chem. Phys., 95, 1852 (1991)
~100 systems investigated (Rm<3% <15%)
Closed shell-closed shell
NEUTRAL A – NEUTRAL B (polarizabilities αA, αB)
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(Ion charge Z and polarizabilities αI, αN)
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+ vdW
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(repulsion + induction + dispersion)
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non resonant(excimers, dications, …)
resonant at crossing(harpooning, …)
resonant at all R(H2
+,Ar2+, …)
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The configuration interaction in rare gas-oxides, RgO
and in rare gas-halides, RgX
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Rare gas sulfides: the interaction anisotropy
van der Waals + charge transfer
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The electrostatic component is important in systems, such as:
Alkali halides
• Na+ + Cl- (charge—charge) V. Aquilanti, D. Cappelletti, F. Pirani Chem. Phys., 209, 299 (1996)
Excimers
• Kr+ + Cl- (charge—charge) M. Krauss, J. Chem. Phys., 67, 1712 (1977) (charge--quadrupole)
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++
XX++((33P)P)HH++
proton-induced dipoleproton-induced dipole
proton-quadrupoleproton-quadrupoleCoulombCoulomb
XX2+2+((44S)S)HH
dispersiondispersion
inductioninductionexchange repulsionexchange repulsion
electron transfer couplingelectron transfer coupling
HX+2- Double photoionization of HX (X=Cl,Br,I)
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1
Low lying states of molecular dications HX++
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2 4 6
28
30
32
34
36
38
40
42
POT
EN
TIA
L E
NE
RG
Y (
eV)
INTERNUCLEAR DISTANCE (Å)
0 0 2 4 6 0 2 4 6
HCl2+
HBr2+
HI2+
3
1
1
3
1
1
3
1
1
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He*(2He*(211S) + NS) + N22OO
He*He*…… NNO NNO
NNO NNO …… He* He*
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The atom (ion) — molecule case
As usual VAB = Vex.rep.+ Vind + Vdisp + Vch.tr + Velectr = VvdW + Vch.tr. + Velectr
Prototypical examples are: F, Cl – H2 V. Aquilanti et al, JPC A, 105, 2401 (2001) Ar+ - N2 R. Candori et al, JCP, 115, 8888 (2001)
Vch.tr. depends on the overlap between orbitals which exchange the electron
(exponentially decreasing with R and varying with the relative orientation of orbitals involved in the exchange)
Velectr relates to the charge distribution on the molecular frame (obtainable from
ab initio calculations)
VvdW arises from the combination of size repulsion effects (short range) with
dispersion and induction attraction (long range). It is very difficult to assess and to model such component
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22--
++
++
1b1
(2p non bonding orbital)
3a1
(sp2 lone pair orbital)
Atom: VAtom: Vvdwvdw + V + Vch.tr.ch.tr.
Ion: VIon: Vvdwvdw + V + Velectrelectr + V + Vchtrchtr
Atom (ion) - water
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Atom (ion) - benzene
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The atom (ion) — molecule case
The assessment of the strength of the van der Waals component involves again the characterization of its dependence on the molecular polarizability (related to features of the electronic distribution in the HOMO and LUMO orbitals). For small and homonuclear diatoms (H2 , N2 …) the electronic distribution is approximately representable through an ellipsoid whose dimensions depend on the tensor components of the polarizability (a single dispersion-induction center).
For big and homonuclear diatoms (I2 , Br2 …) the electronic distribution is better represented by a combination of ellipsoids defined in terms of molecular polarizability contributions: one associated to the bond and the other to the lone pairs(multiple dispersion-induction centers).
Heteronulear diatoms (HCl, HBr …) fall in the two previous cases.
A polyatomic molecule can be considered as the combination of bond and lone pair components (multiple dispersion-induction centers). For the separability of molecular polarizability into several tensor components see JCP, 32, 502 (1960)
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The atom (ion) — molecule case
The proper modelling of the van der Waals component requires the development of atom (ion)—bond and atom (ion)—lone pair potential models exhibiting two basic features:
• they must involve an unique potential function, defined in terms of few parameters, each one having a specific meaning;
• they must remove, totally or partially, the inadequacies, both at short and at long range, of the “venerable” LJ models
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Atom(ion)-bond formulation of the potential energy function (1)
V (r,) ()m
n(r,) m
rm ()
r
n(r,)
n(r,)
n(r,) m
rm ()
r
m
n(r,) 4.0r
rm ()
2
rm () rmsin2 rm//
cos2
() sin2 // cos2
A B
C
r
m= 6 atomm= 4 ion
CPL, 394, 37 (2004)
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V VAA
VA C
ii1
6 V
A Hii1
6
Two-body interactions
Three body interactions
V VAA
VABC
VA C
ii1
6 V
A Hii1
6 V
A CiCi1i1
6 V
A CiHi6i1
6
Potential energy function: Atom-bz
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Atom(ion)-bond formulation of the potential energy function (2)
VAtom benzene V
A CC
ii1
6 V
A CH
jj1
6
Vion benzene V
ion CC
ii1
6 V
ion CH
jj1
6 V
ion quadrupole
Vi Vel 1
4o
qiqionri ion
Vion quadrupole Vi
i1
18
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Benzene-Ar system
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Benzene-Cl- and Benzene-K+clusters
6.0
4.5
3.0
1.5
0.0
y /
Å
-4.0 -2.0 0.0 2.0 4.0x / Å
-300 meV
6.0
4.5
3.0
1.5
z /
Å
-300 meV
6.0
4.5
3.0
1.5
0.0
y /
Å
4.02.00.0-2.0-4.0x / Å
-114 meV
6.0
4.5
3.0
1.5
z /
Å
-830 meV
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Atom-bond formulation vs ab initio calculations:
the case of K+ – C6H6
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(Benzene)m-ion-Atomn clusters
V VI (benzene)
ii1
m V
Aj (benzene)
ij 1
n
i1
m V
Aj I
j 1
n V
Aj Akk j
n
j 1
n 1
Vion benzene V
ion CC
ii1
6 V
ion CH
jj1
6 V
ion quadrupole
VA benzene V
A CC
ii1
6 V
A CH
jj1
6
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Ar-Bz-Cl- and Ar-Bz-K+clusters: Potential energy surfaces
6.0
4.0
2.0
0.0
-2.0
-4.0
z/ Å
-6.0 -4.0 -2.0 0.0 2.0 4.0 6.0x/ Å
-1060 meV
-980 meV
K+
Only one isomer
Two isomers
4.0
2.0
0.0
-2.0
-4.0
z/ Å
8.06.04.02.00.0-2.0-4.0x/ Å
Cl -
-400 meV
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Ar-Bz-Cl- and Ar-Bz-K+clusters
Ar-Bz-Cl-
Ar-Bz-K+
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The PES’s and related force fields have been extensively exploited in molecular dynamics simulations
DL-POLY programs
Cluster configuration energy (function of Etotal) defined, using the present method, as a sum of fragment contributions
opening of isomerization channels beginning of dissociation
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Conclusions and perspectives
Present investigations open new questions and further perspectives:
- Molecule considered as non-rigid body
crucial is the dependence of VAB on the internal coordinates ri
the basic point is the characterization of the dependence of the polarizability
on ri
- Molecule-Molecule systems
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Empirical study of the polarizability α and its anisotropy Δα/α for diatomic bonds and molecules
α = non bonding electron + bonding electron effective bond excitation contributions contributions order function
The above terms depend on: - the number of non bonding and total valence electrons of Atom 1 || || Atom 2
-polarizability value of Atom 1 and Atom 2
- distance r and equilibrium distance re
The method provides correct values for several homonuclear and heteronuclear bonds
Δα/α defined in a similar way
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N2 – N interaction potential from polarizabilities
r
R
atom-bond model
atom-atom model
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Diatom-diatom interaction potentials from polarizabilities
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Dynamical simulations
•The benzene molecule is considered as a rigid body.
• A time step of 1 fs has been adopted to integrate the equa-tions of the motion.
•Dynamical simulations have been performed in the context of the microcanonical ensemble.
v(t+t/2) v(t-t/2) + t F(t)/mr(t+t) r(t) + t v(t+t/2)
v(t)=0.5*(v(t+t/2) + v(t-t/2))
Ti mivi
2
i1
N
kB f
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Energy contributions vs Etotal
-920.0
-910.0
-900.0
-890.0
-880.0
EK
+-b
z / m
eV
300.0250.0200.0150.0100.050.00.0T/ K
-110.0
-105.0
-100.0
-95.0
-90.0
EK
+-A
r
/ m
eV
-30.00
-25.00
-20.00
-15.00
Ebz
-Ar
/ m
eV
-1040.0 -1000.0 -960.0 -920.0Etotal / meV
Ebz--Ar
EAr--K+
Ebz—K+
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Isomerization (1)
0.25
0.20
0.15
0.10
0.05
tim
e (1
|1)
/ ti
me(
2|0)
275.0270.0265.0260.0255.0250.0245.0240.0
T / K
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Isomerization (2)
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160
140
120
100
80
60
40
20
350300250200150100500
150
150
120
120
120 120
120 90
60 60 60
30 30
90
O
CH3
CH3
Ar
Rcm
cm
0 -267 3.59 70 90
61 -206 3.95 23 0 / 180
69 -198 3.92 0 All
91 -176 4.18 180 All
E /cm-1 Eabs /cm-1 Rcm /Å /deg /deg
112 -155 4.86 120 0 / 180
Isoenergetic countours and main stationary properties of the atom-bond PES of DME-Ar
The points of the 2D cross section have been taken at the minimum along Rcm
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150
100
50
0
350300250200150100500
-19
-19
-19
-19
-20 -20
-21
-21
-21
-21
-23
-23
-23
-
23 -23
-24
-24
-24
-24
-25
-25
-25
-2
6
-26
-27
-27
Isoenergetic countours of the atom-bond PES of H2O-He
The points of the 2D cross section have been taken at the minimum along Rcm
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Comparison between experimental and atom bond spherical average parameters of H2O-He
-23.243.083.44At-bond
-22.193.063.45Exper.
ε / cm-1 / ÅRm / ÅModel
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Comparison between experimental and atom-bond integral and differential cross section of H2O-He