DYNAMICS AROUND CRITICAL FEATURES OF ENERGY LANDSCAPES
DYNAMICS AROUND CRITICAL FEATURES OF ENERGY LANDSCAPES
BRUXELLES N. Vaeck
ORSAY D. Lauvergnat
Y. Justum
B. Lasorne
M. Desouter-Lecomte
LYON M.-C. Bacchus
K. Piechowska
LIEGE G. Dive
I. RESEARCH AREA OF THE TEAM
II. METHODOLOGY
III. CRITICAL REGIONS OF ENERGY LANDSCAPES
IV. OBJECTIVES IN THE RADAM NETWORK
I. RESEARCH AREA OF THE TEAM
II. METHODOLOGY
III. CRITICAL REGIONS OF ENERGY LANDSCAPES
IV. OBJECTIVES IN THE RADAM NETWORK
I. RESEARCH AREAI. RESEARCH AREA
Quantum description of elementary processes in gas phase
1) Electrons: ab initio quantum chemistry calculations of PES
2) Nuclei : wave packet dynamics
Chemical reactivity = exploration of an energy landscape by a wave packet possibly guided by a laser field
Chemical reactivity = exploration of an energy landscape by a wave packet possibly guided by a laser field
Particular regions leading to
quantum effects
Dynamics involving few active degrees
of freedom
Ultrafast processes
t < 1 ps
Ultra fast local quantum dynamicsUltra fast local quantum dynamics
Molecular system H
Segregation between active (q) and inactive (Q) coordinatesq : at least the n principal coordinates involved in the reaction path
II. METHODOLOGY II. METHODOLOGY
Rigid or flexible constraints
Constrained subsystem
Hconstrained+ Dissipation
II. METHODOLOGYII. METHODOLOGY
Select n active coordinates q
Hconstrained nDHconstrained nD
= VnD(q)
ab initio
= VnD(q)
ab initio
+ TnD
+ TnD
Compute a PES VnD(q)
Choose rigid or flexible kinematical model Qeq(q) = Qc or ∂Qeq(q)/∂q ≠ 0
Construct the corresponding constrained KEOTnD
II. METHODOLOGYII. METHODOLOGY
n n
nD i j i eqi ,j 1 i=
ij i2
11H + V (f ( ) f ( ) v( ) )
q q qq
TNUM generates numerically but exactly the values of the coefficients of the differential operators at any grid point.
D. Lauvergnat & A. Nauts, J. Chem. Phys. 116, 8560 (2002)
D. J. Rush et K. B. Wiberg, J. Phys. Chem. A 101, 3143 (1997), J. R. Durig et W. Zhao, J. Phys. Chem. 98, 9202 (1994)S. Sakurai N. Meinander et J. Laane, J. Chem. Phys. 108, 3537 (1998)M. L. Senent, CPL 296, 299 (1998), D. Luckhaus, J. Chem. Phys. 113, 1329 2000
Constrained Hamiltonians
III. CRITICAL FEATURES OF ENERGY LANDSCAPESIII. CRITICAL FEATURES OF ENERGY LANDSCAPES
Rate constant
Tunneling
A. Regions of strong non adiabatic
interaction
A. Regions of strong non adiabatic
interaction
B. Bifurcating regions
B. Bifurcating regions
C. Transition statesC. Transition states
IVR between reaction coordinate and deformationElectron transfer
Ultra fast internal conversion
Conversion of an optical signal into mechanical motion
Non B-O B-O
A. Regions of strong non adiabatic interactionA. Regions of strong non adiabatic interaction
Conical intersectionConical intersection
M.-C. Bacchus
K. Piechowska
CASSCF/cc-pvtz
Avoided crossingAvoided crossing
dCO dCBr or dCCl
M.-C. Bacchus
N. Vaeck
CASSCF/cc-pvdz
V2D
Up funnel
Ultra Fast
decay
Diabatic trapping or up-funnel process
Diabatic trapping or up-funnel process
Paradoxical decrease of product yield at increasing excitation energy
Photoisomerization of the Yellow proteine chromophore (p-trans coumaric acid) in S1 state
up-funnel S1/S2 and turn around towards another channel
C. Ko et al. JACS 125, 12710 (2003)
Avoided crossingAvoided crossing
Coordonnée de réaction
En
erg
ie p
ote
nti
ell
e
R
E
Coordonnée de réaction
En
erg
ie p
ote
nti
ell
e
R
E
CH2
Cl
O
Br
BrCH2CO+Cl
Br+CH2COCl
n*(C-Br) n*(C-Cl)
n*(CO)
h
= 248 nm
Competitive dissociation of bromoacetyl chloride
Experimental branching ratio
Cl:Br = 1.0:0.4
Diabatic trappingDiabatic trapping
A’’A’’
A’A’
C C
HH
O
Cl
Br
CH2
Cl
O
Br
BrCH2CO+Cl
Br+CH2COCl
n*(C-Br) n*(C-Cl)
n*(CO)
hM.D. Person, P.W. Kash & L.J. Butler, J. Chem. Phys. 97, 355 (1992) CISD/STO-3G*
W.-J. Ding et al, Journal Chemical Physics 117, 8745 (2002) CAS(8,7)/6-31G* MRCI
B. Lasorne, et al, J. Chem. Phys. 120, 1271, 2004 CASSCF/cc-pvdz (18)
Diabatic trappingDiabatic trapping
Active coordinates Two 2D subspaces
Spectator modesTwo deformations frozen at the Franck-Condon geometry
Other modes optimized in the first A" excited state
1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4
1.2
1.4
1.6
1.8
2
2.2
2.4
2.6
qx / 10-10 m
q y / 1
0-10 m
diabats in orthogonal coordinates
1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
1
1.2
1.4
1.6
1.8
2
2.2
CBr / 10-10
m
CO/10
-10 m
adiabat 1
1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
1
1.2
1.4
1.6
1.8
2
2.2
CBr / 10-10 m
CO
/ 1
0-10 m
adiabat 2
1.5 2 2.5 3 3.5
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
CCl / 10-10 m
CO
/ 1
0-10 m
adiabat 1
1.5 2 2.5 3 3.5
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
CCl / 10-10 m
CO
/ 1
0-10 m
adiabat 2
1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
1
1.2
1.4
1.6
1.8
2
2.2
CBr / 10-10 m
CO
/ 1
0-10 m
diabats
COCO
COCO
Barrier
Barrier
Seam
Seam
Dynamics of photodissociation
Dynamics of photodissociation
CBrCBr
CClCCl
M.-C. Bacchus
N. Vaeck
CASSCF/cc-pvdz
―: t = 0 ―: 12 fs ―: 24 fs ―: 36 fs ―: 48 fs --: 84 fs --: 96 fs
3 4 5 6 7 8
2.5
3
3.5
4
4.5
5
qx / a.u.
q y /
a.u
.
CO/ CBr subspace
0.1
0.15
0.15
3 4 5 6 7 8
2.5
3
3.5
4
4.5
5
qx / a.u.
q y /
a.u
.
CO/CBr subspace
0.1
0.1
0.15
0.15
0.15
0.15 0.15
0.1
0.15
0.15
Dynamics of photodissociationDynamics of photodissociation
CO CBrCO CBr
Ratio of the dissociative fluxes in
the CO/CBr and CO/CCl sides
Experimental branching ratio
Cl:Br = 1.0:0.4
F-C
Dynamics in excited statesDynamics in excited statesWorks in prospectWorks in prospect
in collaboration with QCEXVAL
University of Valencia, Spain
M. Merchán y L. Serrano-Andrés, J. Am. Chem. Soc. 125, 8108
(2003)
CytosineCytosine
Adenine/(H2O)nAdenine/(H2O)n
H. Kang, K.T. Lee , S.K. Kim, Chem. Phys. Letters 359,
213 (2002).
Pump probe experience on adenine/(H20)n
Bifurcation of valleysBifurcation of valleys
C O
H
HH
B. Bifurcating regions : Valley Ridge Inflection PointB. Bifurcating regions : Valley Ridge Inflection Point
Bifurcation of ridgesBifurcation of ridges
V2D
G. Dive
QCISD 6-31G*
G. Dive
B3LYP 6-31G*
Bifurcating regionsBifurcating regions
Dynamics of a wave packet around a VRI region
V2D
spreadi
ng
Time of spreading in a flat region
Width when entering the VRI region
Curvature of the ridge
Time of flight along the ridge
Lenght of the ridge
Gradient along the ridge
Kinetic energy
Competition between
B. Lasorne, G. Dive, D. Lauvergnat and M. Desouter-Lecomte, J. Chem. Phys. 118, 5831 (2003)
TS2: TS1:
1.9631.6372.895
2.652
P
P
P’
P’
TS1
TS1
TS2
TS2
VRI
VRI
Bifurcating regionsBifurcating regions
Dimerisation of cyclopentadiene
P. Caramella, P. Quadrelli & L. Toma, JACS 124, 1130 (2002)
Bifurcating regionsBifurcating regions
Offers a rich variety of behaviours according to the shape of the wave packet
Key regions for branching ratios in the unsymmetrical case
Key regions in the control by laser field ?
20 40 60 80 100 120 140 160 180
-150
-100
-50
0
50
100
150
Key regions in the control by laser field ?Key regions in the control by laser field ?
TargetWave packet
Target
Target
InitialWave packet
After 500 fs
zz
xx
yy
H transfer
C. Regions around transition states C. Regions around transition states
Reaction coordinate s
V
tunneling
tunneling
Rate constant including tunneling
( )( )
( )
N Ek E
h E
( )E
( )N E
( ) ( - )nD jj
N E N E
by TSWP method using the flux
operator eigenvectors
B. Lasorne, F. Gatti, E. Baloïtcha, H.D. Meyer and M. Desouter-Lecomte, J. Chem.Phys. 2004 In press
0
0.1
0.2
0.3
0.4
0.5
-1 -0.5 0 0.5 1
Reaction coordinate (ua)
Ener
gy (e
V)
H exchange between hydroxyl radical and adenine.
0
0.2
0.4
0.6
0.8
1
1.2
0.2 0.3 0.4 0.5 0.6 0.7 0.8
Energy above reactive complex (eV)
N1D
(E)
Complex absorbing potential
Complex absorbing potential
2
1 1 1
2 ˆ ˆ( ˆ ˆ() 2 ( ) )
D DDE HN E r E Ft HF
1( )
DN E
s = s#
constrained reaction path Hamiltonian
G. Dive B3LYP/6-31G**
Active coordinate : reaction coordinate s
tunneling
2
2 1 ( ) ( ) ( )
s s sT f s f s v s
Hydroxyl radical on nucleobases and ribose.
-1
-0.5
0
0.5
-8 -6 -4 -2 0 2 4 6 8
Coordonnée de réaction
Energie
(eV
)
reaction coordinate
E ev
C1
Works in prospectWorks in prospect Rate constantsRate constants
OUR OBJECTIVES IN THE RADAM NETWORKOUR OBJECTIVES IN THE RADAM NETWORK
Preliminary step: collect data at microscopic levelPreliminary step: collect data at microscopic level
Target :
understand the mechanisms of elementary processes involving quantum effects after irradiation of biomolecules
compute and hopefully control branching ratio and rate of
photodissociation
photoisomerization
electron, proton and H transfer
Target :
understand the mechanisms of elementary processes involving quantum effects after irradiation of biomolecules
compute and hopefully control branching ratio and rate of
photodissociation
photoisomerization
electron, proton and H transfer
Tools :
Quantum dynamics in reduced dimensionality
in fundamental and excited states
including a laser field
dissipative effects
around conical intersections, avoided crossings and bifurcating regions
Tools :
Quantum dynamics in reduced dimensionality
in fundamental and excited states
including a laser field
dissipative effects
around conical intersections, avoided crossings and bifurcating regions
Further step: macroscopic levelFurther step: macroscopic level
Inclusion of these data in kinetic schemes for cellular processes reaction chains or selforganization