Computational Chemistry Exercises #9
18.11.2016
1 Potential Energy Surface Scan
In this exercise we will follow a computational study on the catalyzed Keto-Enol tautomerization of vinyl alcohol / acetaldehyde (“Carboxylic Acid Catalyzed Keto-Enol Tautomerizations in the Gas Phase”, G. da Silva, Angew. Chem. Int. Ed. 2010, 49, 7523-7525).
Complex Enol student01 Keto student02 Enol student03 Keto student04 Enol student05 Keto student06 Enol student07 Keto student08
(a) Draw the bi-molecular complex (see Figure 2 in the paper) using Avogadro. (b) Optimize the structure at B3LYP/6-31G** level of theory. (c) Prepare an input file for a relaxed scan (same level of theory) of the proton transfer using the modredundant option (check the manual page for opt ). Please include the option maxcyc=8 regarding the optimization. (Hint: which geometrical parameter do you need to describe a linear proton transfer from Oxygen(vinyl alcohol) to Oxygen(formic acid)? ) (d) Determine the transition state of the Keto-Enol tautomerization. Draw a reaction pathway including figures, Zero-point corrected energies and Gibbs free energies.
Getting started: • Please install WinSCP, XMING and PuTTY on your harddrive.
• Connect to artemis.unige.ch with your student account. Make sure to enable X11 for- warding in order to use graphical interfaces. Submitting a job with Gaussian:
1. Prepare the input file, e.g. example.com. 2. Copy submission script submit.job into the same directory as your input file. 3. Submit job with the following syntax (nothing else has to be specified) sbatch submit.job example.com 4. Gaussian 09 Help: http://gaussian.com/g_tech/g_ur/g09help.htm Report: Please hand in a one page summary including a short description with tables, your name and date.
1 Angewandte Chemie
DOI: 10.1002/anie.201003530 Keto–Enol Kinetics Carboxylic Acid Catalyzed Keto-Enol Tautomerizations in the Gas Phase** Gabriel da Silva*
Carboxylic acids are the products of incomplete combustion cies, with a series of higher-level wavefunction theory energy and of the atmospheric oxidation of biogenic and anthropo- calculations, up to QCISD(T) theory, performed on the genic volatile organic compounds (VOCs). As such, carbox- B3LYP structures. The G3SX method is broadly accurate for ylic acids are found at high levels throughout the troposphere thermochemistry and kinetics, and both the reaction energies (typically in the ppb range),[1] and are present in combustor and the barrier heights reported here are expected to have an exhaust gases. Carboxylic acids, as hydrogen bond donors and average uncertainty of below 1 kcalmol 1.[6,7] Rate constants acceptors, can form relatively strong complexes with organic for the barrierless association of vinyl alcohol and acetalde- molecules in the gas phase; this is particularly true for organic hyde with formic acid were determined by using variational substrates functionalized with carbonyl, alcohol, and other transition state theory (VTST). The rate constants were heteroatomic groups. There is a great deal of interest in the calculated to be in the range 10 12–10 11 cm3 molecule