Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
文献信息
Antonio G. Martínez, Hans-Ulrich Siehl, Santiago de la Moya
An expeditious procedure for the challenging computation of the free energy barriers (ΔG≠) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)//PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol−1) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol−1. Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Λi) and free energy of reaction (ΔG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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