Herein, we propose a conceptually innovative approach to investigating reaction mechanisms. This study demonstrates the importance of considering explicitly the effects of large amplitude motions, aside from the intrinsic reaction coordinate, when tuning the free energy landscape of reaction pathways. We couple the path collective variables method with DFT-based enhanced sampling simulations to characterize the associative mechanism of the hydrolysis of the methyl phosphate dianion in solution. Importantly, energetics and mechanistic differences are observed when passing from the potential to the free energy surface.
Methyl Phosphate Dianion Hydrolysis in Solution Characterized by Path Collective Variables Coupled with DFT-Based Enhanced Sampling Simulations / Branduardi D.; De Vivo M.; Rega N.; Barone V.; Cavalli A.. - In: JOURNAL OF CHEMICAL THEORY AND COMPUTATION. - ISSN 1549-9618. - STAMPA. - 7:(2011), pp. 539-543. [10.1021/ct100547a]
Methyl Phosphate Dianion Hydrolysis in Solution Characterized by Path Collective Variables Coupled with DFT-Based Enhanced Sampling Simulations
CAVALLI, ANDREA
2011
Abstract
Herein, we propose a conceptually innovative approach to investigating reaction mechanisms. This study demonstrates the importance of considering explicitly the effects of large amplitude motions, aside from the intrinsic reaction coordinate, when tuning the free energy landscape of reaction pathways. We couple the path collective variables method with DFT-based enhanced sampling simulations to characterize the associative mechanism of the hydrolysis of the methyl phosphate dianion in solution. Importantly, energetics and mechanistic differences are observed when passing from the potential to the free energy surface.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.