global warming lecture 3-31-08 dr. steven davishome.olemiss.edu/~cmchengs/global...
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Global Warming Lecture3-31-08
Dr. Steven Davis
Department of Chemistry and BiochemistryUniversity of Mississippi
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Calculation of Potential Energy Surfacesusing
ab initio Quantum Chemistry Techniques
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Potential Energy Surfaces
Plots of Energy vs Nuclear Coordinates
Cartesian Coordinates = 3NInternal Coordinates = 3N-6 or 3N-5
3 translations2-3 rotations
ernal Coordinates are bond lengths and ang
rmal Vibrational Modes Expressed in TermsInternal Coordinates
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- quadratic (harmonic oscillator)
ed - Morse potential (atomic interactions)
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gy
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Occupied orbitals Virtual orbitals
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Tricyclo[3.1.0.02,6]hexane (TC6) Isomerization
Allowed Pathway
MCSCF MCQDPT2 CCSD(T) MP2 B3LYP
Activation Energies in kcal/mol (including ZPE)
TC6 TS (E,Z)-C6D
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TC6 (E,Z)-C6D (E,Z)-C6D (Z,Z)-C6D
TC6 C6D
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C1
C3C4
C5 C6
Plot of Bond Distance vs. Reaction Coordinate
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MP2 Level MCSCF Level
at the MP2 and MCSCF Levels
Occupied Virtual
1.9834 0.0179
1.9783 0.0213
1.9756 0.0225
1.9110 0.0887
Natural Orbital Occupation Numbers
for TS at MCSCF Level
(E,Z)-C6D Intermediate
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TC5 TSC5D
5465
2.4598
1.49581.60871.5334
Forbidden Pathway
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1.9832 1.9765 1.9681
1 9606 1 0597 0 9432
Occupied Molecular Orbitals and Natural Orbital Occupation Numbers
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Tricyclo[4.1.0.02,7]heptane Isomerization
Qin, C. and Davis, S. R. J. Org. Chem. 2003, 68, 9081
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Reaction Summary
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wo Opposing Nineteenth CenturViews of Chemistry
Every attempt to employ mathematical methods in the tudy of chemical questions
must be considered profoundly rational and contrary to the pirit of chemistry. If
mathematical analysis should ver hold a prominent place in hemistry – an aberration
which is happily almost mpossible – it would occasion
rapid and widespread egeneration of that science.”Compte Philosophie Positive 1830.
“The more progress physicasciences make, the more thetend to enter the domain of mathematics, which is a kindcenter to which they all converge. We may even judthe degree of perfection to which a science has arrivedthe facility with which it maysubmitted to calculation.”A. Quetelet, Instructions Populaires sur le Cdes Probabilites, Tarlier, Brussels, 1828.
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CO2 photocatalytic reduction
Venkata Pradeep Indrakanti, J.D.Kubicki, M.M. Maroto-Valer, H.H. SchobertJuly 11, 2007CHEMRAWN-XVII and ICCDU-IX conference on greenhouse gases
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Objectivesentify the intermediate species formed during CO2 photoreductioodeling the excited-state chemistry of CO2 species adsorbed on rious low index surface planes of TiO2 .
est the hypothesis of dopant-induced charge carrier trapping fecting photoactivity by performing photoreactions with various ncentrations of La, Sm and Gd-doped TiO2 as photocatalysts.
udy the intermediates of this photoreduction through spectroscoparacterizations and use computational methods to rroborate/complement spectroscopic data.
Venkata Pradeep Indrakanti, J.D.Kubicki, M.M. Maroto-Valer, H.H. SchobertJuly 11, 2007
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singletB3LYP/6-31+G(d), C2 symmetry
Bond lengths in Å, angles in degrees
Venkata Pradeep Indrakanti, J.D.Kubicki, M.M. Maroto-Valer, H.H. SchobertJuly 11, 2007
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2 9 10 2 (triplet B3LYP/6-31+G(d)
CO3 species (triplet-singlet ™q) = -0.29 e-Bond lengths in Å, angles in degreesVenkata Pradeep Indrakanti, J.D.Kubicki, M.M. Maroto-Valer, H.H. SchobertJuly 11, 2007