Download H - Computing, Theory and Experiments of Dynamics and Kinetics

SymposiuminhonorofProf.A.Laganà
VIRTUALENVIRONMENTSANDDETAILEDSIMULATION
OFMOLECULARPROCESSES
Experimentalandcomputa1onalstudieson
Ion-moleculereac1vecollisions
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
Experimentalandcomputa1onalstudieson
Ion-moleculereac1vecollisions
Barcelona(RDG)
1980, 1982,
1980’...
endof1980’ collaborationintheoryProf.A.Laganà
1991
Li+HClRIOSAcrosssectioncalculationsonparallelcomputers, TheoreticaChimicaActa,A.Laganàetal.
1990’... beginningof2000’
Perugia(RDG)
Cortona,NATOadvancedsummerschool…
firstresearchstay(experimentalProfs.F.
Vecchiocattivi&B.Brunetti)
1993-1993Prof.V.Aquilanti‘hyperquantizationalgorithm”
MolecularDynamicsstudiesA.Laganà...
2015....
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
Congratulations to AntonioLaganà
from….
GDRQs’members
MargaritaAlbertí
JoséMa.Lucas
XavierGiménez
FermínHuarte
JaimedeAndrés
AlbertSolé
MiguelGonzález
RamónSayós
…
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
Experimentalandcomputa1onalstudieson
Ion-moleculereac1vecollisions
Outline
-Experimentalion-moleculereactionsintheeVenergyrange
radiofrequencyguidedionbeam(RF-GIB)technique(mostrecentresults)
-Complementaryabinitioquantumchemistrystructurestudies
(directquasiclassicaltrajectorycalculations)
-ImprovementsintheRF-GIBsetupandfutureperspectives
Coauthors:
AntonioAguilar
JaimedeAndrés
EstefaníaLópezPhDstudent
JoséM.Lucas
MargaritaAlbertí
D.Bassi,D.Ascenzi,P.Tosi(UniversityofTrento(Italy)
J.M.Bofill(UniversityofBarcelona,OrganicChemistryDepartment)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
-Experimentalion-moleculereactionsinthe~ eVenergyrange
radiofrequencyguidedionbeam(RF-GIB)technique(mostrecentresults)
-Complementaryabinitioquantumchemistrystructurestudies
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
!  ~ion-moleculereactionsintheeVenergyrange
radiofrequencyguidedionbeam(RF-GIB)apparatus
gasinlet
reactionchamber
SEM
analyzeranddetection
ionfilter
alkaliions
source
turbopumps(backgroundpressure~ 10-7 -10-6 mbar)
(reaction cell pressure~ 10-6 -10-5 mbar)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
associationion-moleculereactions(adducts)
excitationfunction
C6H6+K+→[K--C6H6 ]+
non-covalentinteractions
...abinitiocalculations,
dynamicsmodels,semiempirical
PESandMDsimulations
CH3-CO-CH3+Li+→[Li--CH3-CO-CH3 ]+ SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
! 
J.AllisonandD.P.Ridge(1976)
!  ...dehydrohalogenationofhalogenatedhydrocarbonsanddehydrationofalcohols
inducedbyalkaliions(M+)...
CnH2n+1X→CnH2n+HXX:halide,OH;H-X:hydrogen
(hydrogenhalideorH2O)
tworeactionschannels,
CnH2n+1X+M+→[M--CnH2n]++HXchannel(1)
→CnH2n+[M—HX]+channel(2)
observedchannels1and2dependonthenatureofbothreactantsandnormallyonlyone
productchannelwasdetectedintheAllison&Ridgelist...
orbothreactionchannelswerenotobserved
moreover,weobservedthedecompositionsreactions
CnH2n+1X+M+→[CnH2n]++HX
channel(3)
[CnH2n]+→ decompositionproductschannel(4)
atmoderatelyhigherenergies
th
SymposiuminhonorofProf.A.Laganà,4-5 November2015,Bettona(Italy)
Measured excitation functions and ab initio potential energy
surface profile along the reaction coordinate for the different
reactive channels observed in K+ + i-C3H7Br collisions
excitationfunctionsinK++i-C3H7Brcollisions
ReactionchannelK++i-C3H7Br→[KC3H6]++HBrwasnotobserved
withenoughconfidence…
PotentialEnergySurface
Gaussian 2013 code,
MP2 level, 6-31 G(p-d)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
Measured excitation functions and ab initio potential energy
surface profile along the reaction coordinate for the different
reactive channels observed in K+ + i-C3H7OH collisions
Eliminationreactionsleadingto[KC3H6]+andKOH+were
notobservedtooccursignificantly
[K-i-C3H7OH]+adductformation
excitation function in K+ + i-C3H7OH collisions Decompositionreaction:
K++i-C3H7OH→C3H7++KOH
PES : Gaussian 2013 code, MP2
level, 6-31 G(p-d)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
!  EstefaníaLópez(PhDstudent)intheLAMPatthe UniversityofTrento
…anotherion-moleculereactionsstudies
interstellarclouds,comets&Titan'satmosphere
Intermediatesofimportantorganicacids
involvethecyanidegroup,…nitrilesorganiccompoundswiththe−C≡Nfunctional
group
Amino Acids
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
C4H5NH+
5 isomers of the C4H5NH+ ion (m/q=68) in Titan’s atmosphere CROTONITRILE
PYRROLE
ALLYLCYANIDE
CYCLOPROPILCYANIDE
METHACRYLONITRILE
...asmoleculesofpotentialprebioticalinterest...
InternationalSymposiumonMolecularBeams,29thJune2015,Segovia(Spain)
Quadrupoltamdemsetup
SOLUTIONINLET
Q1
IONSOURCE
C4H5NH+
PRIMARY
SELECTOR
Q2
Reactive
collisions
Q3
MassAnalyzer
C4H5NH+
m/q=68
IONDETECTION
HighVacuumconditions C4H5N
gasinlet
Vacuumpumpsystem
-HCN
C4H5NH+ + C4H5N
m/z=68
(C4H5N)2H+ m/z=135
m/z=108
C7H9NH+ otherproducts…
measured signals at m/z = 68 and 135 C4H5N+C4H5NH+→C8H10N2H+
neutralandprotonatedcyclopropylcyanide
bothintheirelectronicsingletgroundstate
Equilibriumgeometries
singletgroundstate
Gamess2013,abiniti0RHFandMP2
/6-31G(p,d)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
ThestudyofthegroundsingletPESoftheC8H10N2H+systemdid
notshowanyrelevantinformationinadditiontotheexpected
presenceoftheion-moleculeadductatdifferentlevelsoftheory
consideringsingletclosedshellreferenceconfigurationsbutwe
mustconsidertoo…
…thepoten)allybiradicalcharacterofthecyclopropylcyanide…
…thepossiblesingletopenshellreferenceconfigura6ons
…theinabilityoftheprotonatedcyclopropylcyanidetoopenthe3-carbon
ring…
…thatweareexploringthegroundsingletPESofthesystemattheCASCIlevel
usingsome(xe-,ym.o.)ac6vespace&theIRCmethod…
…thatΨCASCIelectronicwavefunctionscouldbeabletoclearly
showimportantcontributionsfromopenshellelectronic
configurationsifthesearereallyinvolved…
…workisinprogressinthisdirection.
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
howtrajectoriesaredone?
...VENUS-NwChempackageasprovided
byProf.W.L.Hase
VENUS(forQCTcalculations):
Selectionofinitialconditions:
...collisionenergy
...impactparameter
...thermalrotationalenergycontent
...thermalvibrationalenergycontentor
selectingspecificvibrationalstates
...randommolecule-moleculeorientation
...Setofcoordinates(q)andmomenta
(p)fort=0
NwChem(forquantumchemistry
calculations,semiempirical,abinitioor
DFT)
...Someconditionsaregivenforending
trajectories
InternationalSymposiumonMolecularBeams,29thJune2015,Segovia(Spain)
RC_1
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
RC_2
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
RC_3
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
RCorNRC?
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
- ImprovementsinthelocalRF-GIBsetup
andfutureperspectives
…forthegenerationofdifferentatomicandmolecularions
-electronimpactionizationsource/adapted
fromPfeifferVacuumGmbH
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
- ImprovementsintheRF-GIBsetup
andfutureperspectives
…anargongasinlettogetherwithsomeambientair…
Ar+
Ar2+
H2
N+
O+
N2+
O2+
…fromthequadrupolemassspectrum…
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
- ImprovementsintheRF-GIBsetup
andfutureperspectives
…calibrationreactionwithwellknowncross-sectionvalues (Erwin &
Armentrout, J. Chem. Phys. 1985, 83, 166-189 )
Ar+(2P) + H2 (1Σ+g) → HAr+(1Σ+) + H (2Sg)
Ar+,He+,Ne+,
CO+,H2+,N2+,
SO+,SCO+,
N2O+,
NH2COH+,…
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)
Acknowledgements
SpanishMinistryofEconomíayCompetividad
(MINECO)ProjectCTQ2013-41317-P
CatalanAgencyforUniversitiesandresearch/
CatalanResearchCouncil
ConsorcideServeisUniversitarisdeCatalunya
(CSUC)forallocatingcomputertime
Thankyouforyourattention!
SymposiuminhonorofProf.A.Laganà,4-5thNovember2015,Bettona(Italy)