Multiscale Simulations of Reactive Intermediates in
23rd IUPAC Conference on Physical Organic Chemistry (ICPOC23) 3rd – 8th July 2016 • Sydney • Australia
Multiscale Simulations of Reactive Intermediates in Argon Matrices and Organic Solvents E. Sanchez-Garcia,a,* P.Sokkar,a W. Thiel,a P. Nuernbergerb and Wolfram Sanderb a
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany b Ruhr-Universität Bochum, Bochum, Germany *[email protected]
Quantum Mechanics (QM) and QM/MM methods were used to investigate the dynamic behavior of reactive intermediates and unusual species in organic solvents and in rare gas matrices at different temperatures.1-5 Among others, diphenylcarbene (DPC, figure), fluorenylidene (FY), and bis(p-methoxyphenyl)carbene (DMDPC) were investigated. The reaction of DPC with protic solvents like water and methanol was studied in an explicit argon matrix doped with water molecules, in amorphous water ice at 3 K or in mixtures of organic solvents at room temperature. The interactions of FY and DMDPC with water were also investigated. A similar effect to that of protic solvents was found for halogen bond donors CF3X that form very strong complexes with the singlet state of DPC, but only weakly interact with triplet DPC. Like with water or single methanol molecules, this results in a switching of the spin state of DPC. Thus, we predict that for carbenes with small S-T gaps the singlet state should become ground state by hydrogen bonding to solvents like water or methanol, or via halogen bonding. On the methodological side, we recently implemented a hybrid QM/MM/CG multi-resolution approach6 which can reduce computation times by 40-75% relative to fully atomistic DFT/MM calculations. Our approach allows performing more efficiently multi-scale molecular dynamics simulations. In this way, the combination of multi-scale methods with MD simulations emerges as a valuable tool for the study of the dynamic behavior of challenging reactive species like carbenes. 1. 2. 3. 4. 5. 6.
Sander, W.; Roy, S.; Polyak, I.; Ramirez-Anguita, J. M.; Sanchez-Garcia, E. J. Am. Chem. Soc. 2012, 134, 8222−8230. Costa, P.; Fernandez-Oliva, M.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2014, 136, 15625−15630. Costa, P.; Trosien, I.; Fernandez-Oliva, M.; Sanchez-Garcia, E.; Sander, W. Angew. Chem. Int. Ed. 2015, 54, 2656-2660. Costa, P.; Lohmiller, T.; Trosien, I.; Savitsky, A.; Lubitz, W.; Fernandez-Oliva, M.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2016, 138, 1622–1629. Henkel, S.; Costa, P.; Klute, L.; Sokkar, P.; Fernandez-Oliva, M.; Thiel, W.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2016, 138, 1689–1697. Sokkar, P.; Boulanger, E.; Thiel, W.; Sanchez-Garcia, E. J. Chem. Theory Comput. 2015, 11, 1809–1818.
CLC10
Multiscale Simulations of Reactive Intermediates in Argon Matrices and Organic Solvents E. Sanchez-Garcia,a,* P.Sokkar,a W. Thiel,a P. Nuernbergerb and Wolfram Sanderb a
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany b Ruhr-Universität Bochum, Bochum, Germany *[email protected]
Quantum Mechanics (QM) and QM/MM methods were used to investigate the dynamic behavior of reactive intermediates and unusual species in organic solvents and in rare gas matrices at different temperatures.1-5 Among others, diphenylcarbene (DPC, figure), fluorenylidene (FY), and bis(p-methoxyphenyl)carbene (DMDPC) were investigated. The reaction of DPC with protic solvents like water and methanol was studied in an explicit argon matrix doped with water molecules, in amorphous water ice at 3 K or in mixtures of organic solvents at room temperature. The interactions of FY and DMDPC with water were also investigated. A similar effect to that of protic solvents was found for halogen bond donors CF3X that form very strong complexes with the singlet state of DPC, but only weakly interact with triplet DPC. Like with water or single methanol molecules, this results in a switching of the spin state of DPC. Thus, we predict that for carbenes with small S-T gaps the singlet state should become ground state by hydrogen bonding to solvents like water or methanol, or via halogen bonding. On the methodological side, we recently implemented a hybrid QM/MM/CG multi-resolution approach6 which can reduce computation times by 40-75% relative to fully atomistic DFT/MM calculations. Our approach allows performing more efficiently multi-scale molecular dynamics simulations. In this way, the combination of multi-scale methods with MD simulations emerges as a valuable tool for the study of the dynamic behavior of challenging reactive species like carbenes. 1. 2. 3. 4. 5. 6.
Sander, W.; Roy, S.; Polyak, I.; Ramirez-Anguita, J. M.; Sanchez-Garcia, E. J. Am. Chem. Soc. 2012, 134, 8222−8230. Costa, P.; Fernandez-Oliva, M.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2014, 136, 15625−15630. Costa, P.; Trosien, I.; Fernandez-Oliva, M.; Sanchez-Garcia, E.; Sander, W. Angew. Chem. Int. Ed. 2015, 54, 2656-2660. Costa, P.; Lohmiller, T.; Trosien, I.; Savitsky, A.; Lubitz, W.; Fernandez-Oliva, M.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2016, 138, 1622–1629. Henkel, S.; Costa, P.; Klute, L.; Sokkar, P.; Fernandez-Oliva, M.; Thiel, W.; Sanchez-Garcia, E. and Sander, W. J. Am. Chem. Soc. 2016, 138, 1689–1697. Sokkar, P.; Boulanger, E.; Thiel, W.; Sanchez-Garcia, E. J. Chem. Theory Comput. 2015, 11, 1809–1818.
CLC10
