Benzyl Alcohol 2012/07/17. Geometries at the B3LYP/aug-cc-pVTZ level dHOCCdOCC5CrOH relative energy (kcal/mol) including ZPE 1gauche cis54.855.40.9630.0.

Slides:



Advertisements
Similar presentations
Conservation of energy -Energy cannot be created or destroyed-
Advertisements

Excited state calculations for polyene and PPV systems Chao Wu.
Photochemistry Lecture 6 Chemical reactions of electronically excited molecules.
Organic and Biological Chemistry Chapter 25 Organic and Biological Chemistry Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene.
I. Modeling the Reaction between Vinylamine and Singlet Oxygen A Semi-Empirical Molecular Orbital Computational Study.
Computational Spectroscopy II. ab initio Methods from part (d) Electronic Spectra Chemistry 713 Updated: February 20, 2008.
© copyright 2011 William A. Goddard III, all rights reservedCh120a-Goddard-L07,08 Ch120a- Goddard- L01 1 Nature of the Chemical Bond with applications.
MMP A Driver’s Guide to Photochemistry: Roads (ie. Surfaces), Crossings and Intersections (A Discussion of MMP ) Tracy Morkin November.
Benzene & Aromatic Compounds By: Dr. Shatha alaqeel
Alkanes Acyclic: CnH2n+2 Cyclic (one ring): CnH2n
Homework #6 The compound HOCl (hypochlorous acid) reacts with the compound C6H5CH3 (toluene) under the influence of ultraviolet light as shown in the following.
Atomic Spectroscopy: Atomic Emission Spectroscopy Atomic Absorption Spectroscopy Atomic Fluorescence Spectroscopy * Elemental Analysis * Sample is atomized.
UV-Vis spectroscopy Electronic absorption spectroscopy.
Spectroscopy nuclear magnetic resonance. The nmr spectra included in this presentation have been taken from the SDBS database with permission. National.
Structures and Properties of Bowl-Shaped Compounds
Give the formula and structure of the compound with this IR and a molecular ion peak at 116.
Theoretical Study of Photodissociation dynamics of Hydroxylbenzoic Acid Yi-Lun Sun and Wei-Ping Hu* Department of Chemistry and Biochemistry, National.
SECOND (PLANAR) MOMENTS AND THEIR APPLICATIONS IN SPECTROSCOPY Robert K. Bohn 1, John A. Montgomery, Jr. 2, H. Harvey Michels 2, Jason Byrd 2 1. Univ.
Kirin 2012/11/30. reaction pathways at different methods 2.
T: +27(0) | | DFT Studies of Photochromic Mercury Complexes Karel G von Eschwege & Jeanet Conradie.
Isomers, Lewis Structures, Connectivity and Sigma Bonds.
Pulsed Field Ionization-Zero Electron Kinetic Energy (PFI-ZEKE) Spectroscopy of Sc-C 6 H 5 X(X=F,CH 3,OH) Complexes Changhua Zhang, Serge A. Krasnokutskia.
Applications I: Partial Charges and Potential Energy Surface Scans Lecture CompChem 5 Chemistry 347 Hope College.
Elucidation of Proton Assisted Fluxionality in Transition-Metal Oxide (TMO) Clusters Raghunath O. Ramabhadran Indiana University, Bloomington 1.
POLARITY OF MOLECULES Molecules can also be described as either polar or nonpolar. nonpolar molecule polar When the individual dipole moments associated.
Electronic Structure of Oxyallyl Diradical: A Photoelectron Spectroscopic Study Takatoshi Ichino, Rebecca L. Hoenigman, Adam J. Gianola, Django H. Andrews,
Chapter 1: Structure and Bonding mcmurry. Coverage: 1. Electron Configurations. 2. Lewis Structures 3. Covalent and Ionic bonds 4. Atomic and Molecular.
Predict which of the following compounds would be the strongest acid.
My first Gaussian input
The Low-Lying States of SF n Species (n=1-6): Insights into Hypervalency from the Recoupled Pair Bonding Model David E. Woon & Thom H. Dunning, Jr. RJ07.
Speaker: ke An Advisor: Jun Zhu A Direct Energetic Measure of Aromaticity Based on a Cleavage of the Rings in Cyclic Compounds.
METO 637 Lesson 4. Electronically Excited Species Electronically excited species can be formed as the result of optical pumping, photo- fragmentation,
Hybridization of Carbon
Electron Transition Can electrons move between energy levels? If so, how? How are transition and light related?
Electronic States of Atoms Quantum numbers for electronsQuantum numbers for many-electron atoms l: orbital angular momentum quantumL: orbital angular.
2008 International Symposium on Molecular Spectroscopy Anion Photoelectron Spectra of CHX 2 - and CX 2 - Properties of the Corresponding Neutrals Scott.
Supplementary material for: Formation Pathways of MSEA from DMS-OH in the Presence of O 2 : A Theoretical Study JUAN M. RAMÍREZ-ANGUITA, ÀNGELS GONZÁLEZ-LAFONT*,
Organic Chemistry By Dr. Mehnaz Kamal Assistant Professor, Pharmaceutical Chemistry Prince Sattam Bin Abdulaziz University.
QM2 Concept test 4.1 Choose all of the following statements that are correct. (1) If the spatial wave function of a two-particle system is symmetric, the.
Problem 1 3 peaks (8 C) means considerable symmetry
HUI LIU, JINJUN LIU, Department of Chemistry, HEMANT M. SHAH and BRUCE W. ALPHENAAR, Department of Electrical & Computer Engineering, University of Louisville.
Benzene & Aromatic Compounds
Valence Bond Theory: Getting New Geometries From Atomic Orbitals 2 p y = C sp 3 hybrid orbital 2 s orbital C 2 p z CH 4 : Tetrahedral 2 p x.
Bonding in methane The simplest alkane, methane, has the molecular formula CH 4. Justify that formula. Write the electronic configuration of carbon and.
Hybridization Carbon configuration Carbon in excited state can form 4 bonds.
Spectroscopy nuclear magnetic resonance.
T. I. Burganov, S. A. Katsyuba, N. A. Zhukova, V. A. Mamedov, Ch
Ch 9 – Covalent Bonding: Orbitals
Suggested Problems: 4-39,41,44–46,54
Chapter 3 Reactions of Alkanes
Carbon Compounds.
Quantum Dynamics Studies of the Vibrational States of HO3(X2A”)
CHM 102 Sinex Enthalpy CHM 102 Sinex.
Electrons orbit the nucleus only within allowed energy levels.
On the activation mechanism of Sn to the EER of ethanol: decomposition of H2O and ethanol over PtnM clusters Yixuan Wang, Albany State University, Albany,
Ch 9 – Covalent Bonding: Orbitals
CH 6-4 SN1 Reaction – Part I SN1: “Substitution….Nucleophilic….Unimolecular (RLS)” Rate = k [substrate] (1st order reaction)
Ch. 4/5 Notes Day 5 2/2/16.
18.2 Valence bond theory: hybridized orbitals and polyatomic molecules
Links Keywords C3 Chemical Reactions 
Lecture 6 January 18, 2012 CC Bonds diamond, ΔHf, Group additivity
Adsorption and Protonation of CO2 on Partially Hydroxylated γ-Al2O3 Surfaces: A Density Functional Theory Study Yunxiang Pan, Chang-jun Liu and Qingfeng.
II. Bohr Model of the Atom (p )
Chapter 1B Carbon Compounds and Chemical Bonds
Fall 2014 Exam III 1. d 9. a 16. (next slides)
Organic Photochemistry
Synthesis of Heterocyclic Rings 5 (carbenes and nitrenes)
Functional Groups.
B-outer-well- region “Jump effect”??? WHY?. B-outer-well- region “Jump effect”??? WHY?
Review of Carbon Classification
Presentation transcript:

Benzyl Alcohol 2012/07/17

Geometries at the B3LYP/aug-cc-pVTZ level dHOCCdOCC5CrOH relative energy (kcal/mol) including ZPE 1gauche cis   planar (gauche cis) (planar) (Cs symmetry) 1

Dissociation pathways in the ground state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the parentheses 2 C 6 H 5 CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state 3 pathway 1: benzyl alcohol → C 6 H 5 CH 2 O + H reaction energy B3LYP/6-31G90.2 B3LYP/6-311+G**119.0 B3LYP/aug-cc-pVTZ97.8 M06-2X/6-311+G** SP101.2 MP2/aptz SP108.0 CCSD(T)/ptz SP101.4 MLSE(C1)-M06-2X104.4 paper_G3(MP2,CCSD)102.9 pathway 2: benzyl alcohol → C 6 H 5 CHOH + H reaction energy B3LYP/6-31G79.3 B3LYP/6-311+G**100.3 B3LYP/aug-cc-pVTZ77.9 M06-2X/6-311+G** SP82.1 MP2/aptz SP106.0 CCSD(T)/ptz SP83.6 MLSE(C1)-M06-2X84.8 paper_G3(MP2,CCSD)84.4 pathway 3: benzyl alcohol → C 6 H 5 CH 2 + OH reaction energy B3LYP/6-31G69.2 B3LYP/6-311+G**94.7 B3LYP/aug-cc-pVTZ73.0 M06-2X/6-311+G** SP82.1 MP2/aptz SP110.8 CCSD(T)/ptz SP80.6 MLSE(C1)-M06-2X83.4 paper_G3(MP2,CCSD)81.6 pathway 4: benzyl alcohol → C 6 H 5 + CH 2 OH reaction energy B3LYP/6-31G93.7 B3LYP/6-311+G**111.1 B3LYP/aug-cc-pVTZ88.7 M06-2X/6-311+G** SP97.4 MP2/aptz SP128.1 CCSD(T)/ptz SP99.3 MLSE(C1)-M06-2X101.1 paper_G3(MP2,CCSD)98.4

Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state 4 pathway 5: benzyl alcohol → C 6 H 6 + CH 2 O barrierreaction energy B3LYP/6-31G B3LYP/6-311+G** B3LYP/aug-cc-pVTZ M06-2X/6-311+G** SP MP2/aptz SP CCSD(T)/ptz SP MLSE(C1)-M06-2X paper_G3(MP2,CCSD) pathway 6: benzyl alcohol → C 6 H 5 CH(singlet, triplet) + H 2 O barriercomplexreaction energy C 6 H 5 CH(S) + H 2 OC 6 H 5 CH(T) + H 2 O B3LYP/6-31G B3LYP/6-311+G** B3LYP/aug-cc-pVTZ M06-2X/6-311+G** SP MP2/aptz SP CCSD(T)/ptz SP MLSE(C1)-M06-2X paper_G3(MP2,CCSD) C 6 H 5 CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

Possible excited states of dissociation products photo energy: kcal/mol 5 pathway 1: benzyl alcohol → C 6 H 5 CH 2 O + H reaction energy: kcal/mol 以 doublet state C 6 H 5 CH 2 O 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH 2 O ground state A" Excited state 1 A" Excited state 2 A' Excited state 3 A' eV kcal/mol pathway 2: benzyl alcohol → C 6 H 5 CHOH + H reaction energy: 83.6 kcal/mol 以 doublet state C 6 H 5 CHOH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CHOH ground state A" Excited state 1 A' Excited state 2 A' Excited state 3 A" eV kcal/mol pathway 3: benzyl alcohol → C 6 H 5 CH 2 + OH reaction energy: 80.6 kcal/mol 以 doublet state C 6 H 5 CH 2 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH 2 ground state B1 Excited state 1 B2 Excited state 2 A1 eV kcal/mol

6 Possible excited states of dissociation products photo energy: kcal/mol pathway 6: benzyl alcohol → C 6 H 5 CH + H 2 O reaction energy: 77.5(S), 74.3(T) kcal/mol 以 triplet state C 6 H 5 CH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH Triplet ground state-A" Excited state 1 A' Excited state 2 A' eV kcal/mol 以 singlet state C 6 H 5 CH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH Triplet ground state-A" Singlet ground state-A' Excited state 1 Singlet-A" Excited state 2 Triplet-A' Excited state 3 Triplet-A' Excited state 4 Triplet-A" eV  kcal/mol 

Dissociation pathways in the triplet state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the parentheses 7

Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state 8 benzyl alcohol(singlet) → benzyl alcohol(triplet) S-T gap B3LYP/6-31G82.5 B3LYP/6-311+G**101.7 B3LYP/aug-cc-pVTZ80.4 M06-2X/6-311+G** SP86.3 MP2/aptz SP106.5 MP2/ptz SP106.8 CCSD(T)/ptz SP96.9 MLSE(C1)-M06-2X85.9 paper_G3(MP2,CCSD)85.3 pathway 1: benzyl alcohol → C 6 H 5 + CH 2 OH barrierreaction energy B3LYP/6-31G B3LYP/6-311+G** B3LYP/aug-cc-pVTZ M06-2X/6-311+G** SP MP2/aptz SP CCSD(T)/ptz SP MLSE(C1)-M06-2X paper_G3(MP2,CCSD) pathway 2: benzyl alcohol → C 6 H 5 CHOH + H barrierreaction energy B3LYP/6-31G79.3 B3LYP/6-311+G**100.3 B3LYP/aug-cc-pVTZ77.9 M06-2X/6-311+G** SP82.1 MP2/aptz SP106.0 CCSD(T)/ptz SP83.6 MLSE(C1)-M06-2X84.8 paper_G3(MP2,CCSD)

Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state 9 pathway 3: benzyl alcohol → C 6 H 5 CH 2 O + H barrierreaction energy B3LYP/6-31G90.2 B3LYP/6-311+G**119.0 B3LYP/aug-cc-pVTZ97.8 M06-2X/6-311+G** SP101.2 MP2/aptz SP108.0 CCSD(T)/ptz SP101.4 MLSE(C1)-M06-2X104.4 paper_G3(MP2,CCSD) pathway 4: benzyl alcohol → C 6 H 5 CH 2 + OH barriercomplexreaction energy B3LYP/6-31G B3LYP/6-311+G** B3LYP/aug-cc-pVTZ M06-2X/6-311+G** SP MP2/aptz SP CCSD(T)/ptz SP MLSE(C1)-M06-2X paper_G3(MP2,CCSD)

The energies (kcal/mol) along the O-H bond distance in hydroxyl group of the planar conformation 10

The energies (kcal/mol) along the O-H bond distance in hydroxyl group of the gauche cis conformation 11