Electronic and Inertial Effects of Methylation on Excited-State Hydrogen Transfer

Here you will find the dataset related to the article entitled: Electronic and Inertial Effects of Methylation on Excited-State Hydrogen Transfer ------------------------------------------------------------------------------ critical_points_geometries.tar.gz This repository contains the XYZ files of the critical points for malonaldehyde (MA) and acetylacetone (AcAc) computed at the SA3/SA2-XMS(Re=0.3)-CASPT2(14,12)/cc-pVDZ (msmr) and SA3/SA2-XMS(Im=0.3)-CASPT2(10,8)/cc-pVDZ (sssr) levels of theory. Notation: MA - Malonaldehyde AcAc - Acetylacetone S0min - Minimum of S0 electronic state S1min - Minimum of S1 electronic state T1min - Minimum of T1 electronic state S1-TS - Transition state on S1 S2S1_twist - Twisted S2/S1 minimum energy conical intersection S1S0_twist - Twisted S1/S0 minimum energy conical intersection S1/S0-CIPyrC - Twist-pyramidalized conical intersection extracted from representative surface hop in the FSSH simulations and optimized to relax the structure to the seam To describe the conformational variations along the H-transfer intersection seam, we adopt a naming convention based on: Whether the methyl groups are staggered (S) or eclipsed (E), where S designates the staggered conformer in which the keto-side methyl has a C–H bond oriented in the same direction as the adjacent C=O bond For the eclipsed conformer, whether a C–H bond of each methyl group points in the same direction as the C–O bonds (u, up) or in the opposite direction (d, down) Whether the enolic H-atom is positioned symmetrically (sym) or asymmetrically (asym) relative to the O-atoms Computational details and extra information regarding these structures can be found in the main text and supporting information of the article. ------------------------------------------------------------------------------ FSSH_ICs.tar.gz This repository contains all the initial conditions (ICs) sampled from quantum-thermostat AIMD and used to perform decoherence-corrected fewest-switches surface hopping dynamics simulations of MA and AcAc. All IC files are named as IC_XXXXX.txt where XXXXX = IC number Filenames including "_discarded" resulted in dynamics that did not satisfy the trajectory monitoring criteria. Each IC file contains the cartesian coordinates, and the corresponding nuclear velocities in their respective atomic units.