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Solvent Induced Proton Polarization within the Nuclear–Electronic Orbital Framework

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [3];  [3];  [2]
  1. University of Washington, Seattle, WA (United States); Yale University
  2. University of Washington, Seattle, WA (United States)
  3. Yale University, New Haven, CT (United States)
+ Show Author Affiliations
To explicitly account for nuclear quantum effects and solvent environments in simulations of chemical processes, the nuclear-electronic orbital approach is coupled with a polarizable continuum model (PCM). This NEO–PCM approach is used to explore the influence of solvation on nuclear polarization through applications to a water dimer and a set of protonated water tetramers. Nuclear polarization in these species is analyzed in terms of changes in proton density and oxygen–hydrogen bond length. Solvation is shown to enhance nuclear polarization with increasing dielectric constant. For the water dimer, the internal, hydrogen-bonded proton is shown to polarize more than the external, free proton. Moreover, proton quantization leads to greater solvent polarization through their mutual polarization. Furthermore, these calculations highlight the complex interplay among electronic, nuclear, and solvent polarization in chemical systems.
Research Organization:
University of Washington, Seattle, WA (United States); Yale University, New Haven, CT (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0023284
OSTI ID:
1974722
Alternate ID(s):
OSTI ID: 2554027
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 12 Vol. 14; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Electrical properties
Polarization
Reaction mechanisms
Solvation
Solvents