Origin of the inverse temperature dependence of hydrophobic attraction

Using enhanced sampling techniques, we have precisely characterized the water-mediated interactions between nanometer-sized spherical hydrophobic solutes. The interaction potential is captured with remarkable accuracy by a tailored morphometric theory that distills and integrates essential physical...

Full description

Saved in:
Bibliographic Details
Main Authors: Nigel B. Wilding, Francesco Turci
Format: Article
Language:English
Published: American Physical Society 2025-06-01
Series:Physical Review Research
Online Access:http://doi.org/10.1103/66lz-1yw9
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849710643489275904
author Nigel B. Wilding
Francesco Turci
author_facet Nigel B. Wilding
Francesco Turci
author_sort Nigel B. Wilding
collection DOAJ
description Using enhanced sampling techniques, we have precisely characterized the water-mediated interactions between nanometer-sized spherical hydrophobic solutes. The interaction potential is captured with remarkable accuracy by a tailored morphometric theory that distills and integrates essential physical properties of the solvation shell. Notably, our simulations successfully replicate a previously poorly understood phenomenon: the anomalous strengthening of hydrophobic attraction with rising temperature. Our theory pinpoints the origin of this “inverse temperature” effect in the rapid thermal expansion of the solvation shell, a process driven by a critical drying transition. Intriguingly, this effect becomes increasingly pronounced with stronger solute-water van der Waals attraction, i.e., decreasing hydrophobicity—a subtle yet significant feature accounted for by our theory.
format Article
id doaj-art-b1f048722b38458ebdcc1998a5804de6
institution DOAJ
issn 2643-1564
language English
publishDate 2025-06-01
publisher American Physical Society
record_format Article
series Physical Review Research
spelling doaj-art-b1f048722b38458ebdcc1998a5804de62025-08-20T03:14:50ZengAmerican Physical SocietyPhysical Review Research2643-15642025-06-0172L02207910.1103/66lz-1yw9Origin of the inverse temperature dependence of hydrophobic attractionNigel B. WildingFrancesco TurciUsing enhanced sampling techniques, we have precisely characterized the water-mediated interactions between nanometer-sized spherical hydrophobic solutes. The interaction potential is captured with remarkable accuracy by a tailored morphometric theory that distills and integrates essential physical properties of the solvation shell. Notably, our simulations successfully replicate a previously poorly understood phenomenon: the anomalous strengthening of hydrophobic attraction with rising temperature. Our theory pinpoints the origin of this “inverse temperature” effect in the rapid thermal expansion of the solvation shell, a process driven by a critical drying transition. Intriguingly, this effect becomes increasingly pronounced with stronger solute-water van der Waals attraction, i.e., decreasing hydrophobicity—a subtle yet significant feature accounted for by our theory.http://doi.org/10.1103/66lz-1yw9
spellingShingle Nigel B. Wilding
Francesco Turci
Origin of the inverse temperature dependence of hydrophobic attraction
Physical Review Research
title Origin of the inverse temperature dependence of hydrophobic attraction
title_full Origin of the inverse temperature dependence of hydrophobic attraction
title_fullStr Origin of the inverse temperature dependence of hydrophobic attraction
title_full_unstemmed Origin of the inverse temperature dependence of hydrophobic attraction
title_short Origin of the inverse temperature dependence of hydrophobic attraction
title_sort origin of the inverse temperature dependence of hydrophobic attraction
url http://doi.org/10.1103/66lz-1yw9
work_keys_str_mv AT nigelbwilding originoftheinversetemperaturedependenceofhydrophobicattraction
AT francescoturci originoftheinversetemperaturedependenceofhydrophobicattraction