Ab initio molecular dynamics study of crystalline nitric acid trihydrate

Doris M. Sullivan, Ken Bagchi, Mark Tuckerman, Michael L. Klein

Research output: Contribution to journalArticle

Abstract

Ab initio based Car-Parrinello molecular dynamics calculations (CPMD) have been used to investigate the properties of crystalline nitric acid trihydrate (NAT) at 195 K. The crystal unit cell consists of four formula units of NAT and nominally contains the ions NO3- and H3O+ plus H2O molecules. Reversible protontransfer events were observed between unique H3O+and neighboring H2O pairs, which occur throughout the crystal. Full proton transfer to form a new neighboring H3O+ molecule was a rare event. The motion of this mobile proton was associated with hyperextension of the covalent oxygen-hydrogen of H3O+, whose stretch frequency was observed in corresponding power spectra. Calculations showed that a classical free energy of 3.3 kBT was required for the proton to reach the center of the oxygen-oxygen pair. Crystalline NAT was further characterized by calculated equilibrium averages, structural properties, and vibrational spectra.

Original languageEnglish (US)
Pages (from-to)8678-8683
Number of pages6
JournalJournal of Physical Chemistry A
Volume103
Issue number43
StatePublished - 1999

Fingerprint

Nitric Acid
nitric acid
Molecular dynamics
Oxygen
molecular dynamics
Crystalline materials
protons
Protons
oxygen
Crystals
Molecules
Proton transfer
Vibrational spectra
Power spectrum
vibrational spectra
Free energy
crystals
power spectra
Structural properties
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ab initio molecular dynamics study of crystalline nitric acid trihydrate. / Sullivan, Doris M.; Bagchi, Ken; Tuckerman, Mark; Klein, Michael L.

In: Journal of Physical Chemistry A, Vol. 103, No. 43, 1999, p. 8678-8683.

Research output: Contribution to journalArticle

Sullivan, DM, Bagchi, K, Tuckerman, M & Klein, ML 1999, 'Ab initio molecular dynamics study of crystalline nitric acid trihydrate', Journal of Physical Chemistry A, vol. 103, no. 43, pp. 8678-8683.
Sullivan, Doris M. ; Bagchi, Ken ; Tuckerman, Mark ; Klein, Michael L. / Ab initio molecular dynamics study of crystalline nitric acid trihydrate. In: Journal of Physical Chemistry A. 1999 ; Vol. 103, No. 43. pp. 8678-8683.
@article{ebcb24464452479cbb9db0e14f44487d,
title = "Ab initio molecular dynamics study of crystalline nitric acid trihydrate",
abstract = "Ab initio based Car-Parrinello molecular dynamics calculations (CPMD) have been used to investigate the properties of crystalline nitric acid trihydrate (NAT) at 195 K. The crystal unit cell consists of four formula units of NAT and nominally contains the ions NO3- and H3O+ plus H2O molecules. Reversible protontransfer events were observed between unique H3O+and neighboring H2O pairs, which occur throughout the crystal. Full proton transfer to form a new neighboring H3O+ molecule was a rare event. The motion of this mobile proton was associated with hyperextension of the covalent oxygen-hydrogen of H3O+, whose stretch frequency was observed in corresponding power spectra. Calculations showed that a classical free energy of 3.3 kBT was required for the proton to reach the center of the oxygen-oxygen pair. Crystalline NAT was further characterized by calculated equilibrium averages, structural properties, and vibrational spectra.",
author = "Sullivan, {Doris M.} and Ken Bagchi and Mark Tuckerman and Klein, {Michael L.}",
year = "1999",
language = "English (US)",
volume = "103",
pages = "8678--8683",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "43",

}

TY - JOUR

T1 - Ab initio molecular dynamics study of crystalline nitric acid trihydrate

AU - Sullivan, Doris M.

AU - Bagchi, Ken

AU - Tuckerman, Mark

AU - Klein, Michael L.

PY - 1999

Y1 - 1999

N2 - Ab initio based Car-Parrinello molecular dynamics calculations (CPMD) have been used to investigate the properties of crystalline nitric acid trihydrate (NAT) at 195 K. The crystal unit cell consists of four formula units of NAT and nominally contains the ions NO3- and H3O+ plus H2O molecules. Reversible protontransfer events were observed between unique H3O+and neighboring H2O pairs, which occur throughout the crystal. Full proton transfer to form a new neighboring H3O+ molecule was a rare event. The motion of this mobile proton was associated with hyperextension of the covalent oxygen-hydrogen of H3O+, whose stretch frequency was observed in corresponding power spectra. Calculations showed that a classical free energy of 3.3 kBT was required for the proton to reach the center of the oxygen-oxygen pair. Crystalline NAT was further characterized by calculated equilibrium averages, structural properties, and vibrational spectra.

AB - Ab initio based Car-Parrinello molecular dynamics calculations (CPMD) have been used to investigate the properties of crystalline nitric acid trihydrate (NAT) at 195 K. The crystal unit cell consists of four formula units of NAT and nominally contains the ions NO3- and H3O+ plus H2O molecules. Reversible protontransfer events were observed between unique H3O+and neighboring H2O pairs, which occur throughout the crystal. Full proton transfer to form a new neighboring H3O+ molecule was a rare event. The motion of this mobile proton was associated with hyperextension of the covalent oxygen-hydrogen of H3O+, whose stretch frequency was observed in corresponding power spectra. Calculations showed that a classical free energy of 3.3 kBT was required for the proton to reach the center of the oxygen-oxygen pair. Crystalline NAT was further characterized by calculated equilibrium averages, structural properties, and vibrational spectra.

UR - http://www.scopus.com/inward/record.url?scp=0001624503&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001624503&partnerID=8YFLogxK

M3 - Article

VL - 103

SP - 8678

EP - 8683

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 43

ER -