Computational Chemistry Exercises #9

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 kcalmolÀ1.[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 10À12–10À11 cm3 moleculeÀ1 sÀ1, ability of hydrogen-bound complexes to influence the kinetics and are relatively insensitive to the temperature (consistent and the products of gas-phase reactions.[2,3] For example, it has with a barrierless process). The VTST calculations were been demonstrated that a water molecule bound to acetalde- performed on G3SX level potential energy profiles (see the hyde (a complex with a bond dissociation energy of approx- Supporting Information for a detailed description of the imately 5 kcalmolÀ1) increases the rate of hydrogen abstrac- calculations). The apparent rate constants in the chemically tion by the hydroxyl (OH) radical.[3] This finding is supported activated vinyl alcohol + formic acid ! acetaldehyde + by theoretical calculations, which reveal that water facilitates, formic acid process (and in the slower reverse reaction) are but does not directly participate in, the hydrogen-abstraction determined as a function of temperature and pressure by reaction. solving the time-dependent master equation, with RRKM Herein we demonstrate that carboxylic acids catalyze theory for microcanonical rate constants, k(E). Initial calcu- intramolecular hydrogen shifts in the gas phase, through the lations between 0.01–100 atm revealed these reactions to be initial formation of a hydrogen bonded complex followed by a insensitive to pressure, and all the reported values are double-hydrogen-shift (DHS) reaction. The transfer of hydro- calculated at 1 atm. For the double-hydrogen-shift step, gen atoms within and between molecules is ubiquitous in gas- tunneling corrections are applied using an Eckart barrier, phase reactions, and the generic DHS mechanism reported approximated from the imaginary vibrational frequency of here has the potential to influence a wide range of reaction the transition state (1354.3 cmÀ1) and the 0 K forward and processes. This study uses quantum chemistry and statistical reverse reaction barriers. Master equation calculations are reaction rate theory techniques to calculate the rate constants performed with an energy grain of 0.1 kcalmolÀ1,uptoa for the formic acid catalyzed conversion of vinyl alcohol maximum energy of 100 kcalmolÀ1. Lennard-Jones parame- (ethenol) to acetaldehyde, that is, the simplest keto–enol ters for the active C3H6O3 isomers are 5.4 and 400 K, where tautomerization. Furthermore, we demonstrate that this energy transfer is treated using an exponential-down model À1 process is competitive with photochemical oxidation of the with DEdown = 1000 cm . Nitrogen was used as the bath gas. enol. Enols, which are the less stable isomers of carbonyl The rate constants calculated for the forward and reverse n compounds, have recently emerged as significant combustion reaction processes are reported in the form k = A’T exp(ÀEa/ intermediates,[4] and are implicated in the photochemical RT), where k and A’Tn are in cm3 moleculeÀ1 sÀ1, the [5] À1 oxidation of isoprene. activation energy Ea is in calmol , and the temperature T Quantum chemical calculations are performed at the in K. All the electronic structure theory calculations are composite G3SX level of theory.[6] This theoretical method performed using Gaussian03,[8] and the rate constant calcu- uses B3LYP/6-31G(2df,p) structures and vibrational frequen- lations are conducted with the software ChemRate 1.5.9.[9] The transition-state structure for the formic acid catalyzed conversion of vinyl alcohol to acetaldehyde is shown in [*] Dr. G. da Silva Figure 1 (with imaginary frequency displacement vectors). Department of Chemical and Biomolecular Engineering The corresponding enthalpy profile for this reaction is shown The University of Melbourne in Figure 2, where the uncatalyzed unimolecular reaction is Melbourne, Victoria 3010 (Australia) E-mail: [email protected] also illustrated. Note that the use of carboxylic acids other [**] Computational resources provided by the Victorian Partnership for than formic acid has a negligible effect on both the transition- Advanced Computing (VPAC) . This work was presented in part at state structure and on the reaction energetics. Figure 1 shows the 2009 Fall Meeting of the AGU. that the DHS process involves concerted movement of two Supporting information for this article is available on the WWW hydrogen atoms, thus resulting in proton exchange between under http://dx.doi.org/10.1002/anie.201003530. the reactants. However, the net effect is the transformation of Angew. Chem. Int. Ed. 2010, 49, 7523 –7525 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 7523 Communications same oxygen atom within a molecule, although in this case the transition state is considerably strained, while the participat- ing oxygen atom has a three-coordinated bonding motif (demonstrated for vinyl alcohol + H2O in the Supporting Information). As a result, the barrier is relatively large, with a modest catalytic effect. Rate constants have been calculated for the chemically activated vinyl alcohol + formic acid, ! acetaldehyde + formic acid reaction (as well as for the reverse process) from 300 to 2000 K at 1 atm, and are plotted in Figure 3. Although Figure 1. Double-hydrogen-shift (DHS) transition state in the reaction of vinyl alcohol with formic acid (B3LYP/6-31G(2df,p). Figure 3. Calculated rate constants for the formic acid catalyzed conversion of vinyl alcohol to acetaldehyde, and vice versa. Filled circles: CH3CHO!CH2CHOH; empty circles: CH2CHO!CH3CHO. the reverse dissociation of the initially activated [C3H6O3]* adduct is the major process in the reaction between vinyl alcohol and formic acid, branching to form the acetaldehyde/ formic acid complex (which promptly dissociates) is also significant, and rate constants for this chemically activated process are still relatively large. The rate constants in the isomerization reaction between vinyl alcohol and formic acid Figure 2. Enthalpy profile for the reaction of vinyl alcohol with formic are essentially independent of temperature, with a small acid (G3SX 298 K enthalpies, kcalmolÀ1). negative activation energy at low temperatures (from the barrierless reaction) and a small positive activation energy at vinyl alcohol into acetaldehyde (or vice versa), thus leaving higher temperatures (resulting from the 5.6 kcalmolÀ1 reac- the carboxylic acid essentially unchanged. We can see from tion barrier). In the reaction between acetaldehyde and Figure 2 that this DHS mechanism reduces the barrier for the

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