TY - JOUR
T1 - Thermodynamics of Hydration from the Perspective of the Molecular Quasichemical Theory of Solutions
AU - Asthagiri, Dilipkumar N.
AU - Paulaitis, Michael E.
AU - Pratt, Lawrence R.
N1 - Funding Information:
We thank our students and colleagues whose works are cited below for enriching our understanding of the theory. We gratefully acknowledge computing support from National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract DE-AC02-05CH11231. We gratefully acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing HPC resources that have contributed to the research results reported within this paper.
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/8/5
Y1 - 2021/8/5
N2 - The quasichemical organization of the potential distribution theorem, molecular quasichemical theory (QCT), enables practical calculations and also provides a conceptual framework for molecular hydration phenomena. QCT can be viewed from multiple perspectives: (a) as a way to regularize an ill-conditioned statistical thermodynamic problem; (b) as an introduction of and emphasis on the neighborship characteristics of a solute of interest; or (c) as a way to include accurate electronic structure descriptions of near-neighbor interactions in defensible statistical thermodynamics by clearly defining neighborship clusters. The theory has been applied to solutes of a wide range of chemical complexity, ranging from ions that interact with water with both long-ranged and chemically intricate short-ranged interactions, to solutes that interact with water solely through traditional van der Waals interations, and including water itself. The solutes range in variety from monatomic ions to chemically heterogeneous macromolecules. A notable feature of QCT is that, in applying the theory to this range of solutes, the theory itself provides guidance on the necessary approximations and simplifications that can facilitate the calculations. In this Perspective, we develop these ideas and document them with examples that reveal the insights that can be extracted using the QCT formulation.
AB - The quasichemical organization of the potential distribution theorem, molecular quasichemical theory (QCT), enables practical calculations and also provides a conceptual framework for molecular hydration phenomena. QCT can be viewed from multiple perspectives: (a) as a way to regularize an ill-conditioned statistical thermodynamic problem; (b) as an introduction of and emphasis on the neighborship characteristics of a solute of interest; or (c) as a way to include accurate electronic structure descriptions of near-neighbor interactions in defensible statistical thermodynamics by clearly defining neighborship clusters. The theory has been applied to solutes of a wide range of chemical complexity, ranging from ions that interact with water with both long-ranged and chemically intricate short-ranged interactions, to solutes that interact with water solely through traditional van der Waals interations, and including water itself. The solutes range in variety from monatomic ions to chemically heterogeneous macromolecules. A notable feature of QCT is that, in applying the theory to this range of solutes, the theory itself provides guidance on the necessary approximations and simplifications that can facilitate the calculations. In this Perspective, we develop these ideas and document them with examples that reveal the insights that can be extracted using the QCT formulation.
UR - http://www.scopus.com/inward/record.url?scp=85112541526&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85112541526&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.1c04182
DO - 10.1021/acs.jpcb.1c04182
M3 - Review article
C2 - 34313434
AN - SCOPUS:85112541526
SN - 1520-6106
VL - 125
SP - 8294
EP - 8304
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 30
ER -