Quantifying Fluctuations of Average Solvent Environments for Embedding Calculations

Article Article scientifique Article Quantifying Fluctuations of Average Solvent Environments for Embedding Calculations eng 2022-01-19 2022-01-19 author Gonzalez Espinoza Cristina 0000-0002-7808-0771 Université de Genève, Départment de Chimie Physique 30, Quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland 909259 author Rumble Christopher Allen 0000-0003-1757-8960 Université de Genève, Départment de Chimie Physique 30, Quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland 877558 author Borgis Daniel 0000-0003-4971-9502 Ecole Normale Supérieure, Départment de Chimie, UMR 8640, PSL University, Sorbonne University, CNRS, 75005 Paris, France 938834 author Wesolowski Tomasz Adam 0000-0001-5792-4616 Université de Genève, Départment de Chimie Physique 30, Quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland 92358 Département de chimie physique (CHIFI) 1072-1088 10.1021/acs.jctc.1c01108 35044168 1549-9618 https://pubs.acs.org/doi/10.1021/acs.jctc.1c01108 The viability and effectiveness of replacing an ensemble of embedded solute calculations by a single calculation using an average description of the solvent environment are evaluated. This work explores the fluctuations of the average description of the system obtained in two ways: from calculations on an ensemble of geometries and from an average environment constructed from the same ensemble. To this end, classical molecular dynamics simulations of a rigid acetone solute in SPCE water are performed in order to generate an ensemble of solvent environments. From this ensemble of solvent configurations, a number of different approaches for constructing an average solvent environment are employed. We perform a thorough numerical analysis of the fluctuations of the electrostatic potential experienced by the solute, as well as the resulting fluctuations of the solute’s electronic density, measured through its dipole moment and fitted atomic point charges. At the same time, we inspect the accuracy of the methods used to construct average environments. Finally, the proposed method for generating the embedding potential from an average environment density is applied to estimate the solvatochromic shift of the first excitation of acetone. In order to account for quantum confinement effects, which may be important in certain cases, the fluctuations in the shift due to the interaction with the solvent are evaluated using frozen-density-embedding theory. Our results demonstrate that, for normally distributed environments, the constructed average environment is a reasonably good representation of a fluctuating molecular solvent environment. We then provide guidance for future comparisons between these theoretical treatments of solute/solvent systems to experimental measurements. Approximation Chemical calculations Embedding Solution chemistry Solvents Dewey 540 38 Département de chimie physique 142 false Journal of chemical theory and computation 18 2 20d0f996-b5ad-4913-9daf-a8b1f1d71c21 Article (Published version) Restricted Article_scientifique_from_crossref-.pdf 4334876 application/pdf 5f9577dab53b5e6ca8aa78ce70529b101d01b978c935eba2b5b14941e5022295 Vignette Public ct1c01108_0017.webp 100199 image/png restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

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Quantifying Fluctuations of Average Solvent Environments for Embedding Calculations	Journal of chemical theory and computation			2022	57	0

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Borgis, Daniel