Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Real-space pseudopotential method for computing the vibrational Stark effect

Abstract

The vibrational Stark shift is an important effect in determining the electrostatic environment for molecular or condensed matter systems. However, accurate ab initio calculations of the vibrational Stark effect are a technically demanding challenge. In this paper, we make use of density functional theory constructed on a real-space grid to expedite the computation of this effect. Our format is especially advantageous for the investigation of small molecules in finite fields as cluster boundary conditions eliminate spurious supercell interactions and allow for charged systems, while convergence is controlled by a single parameter, the grid spacing. The Stark tuning rate is highly sensitive to the interaction between anharmonicity in a vibrational mode and the applied field. To ensure this subtle interaction is fully captured, we apply three parallel approaches: a direct finite field, a perturbative method, and a molecular dynamics method. Finally, we illustrate this method by applying it to several small molecules containing C–O and C–N bonds and show that a consistent result can be obtained.

Authors:
 [1];  [2];  [2];  [3]
+ Show Author Affiliations
  1. Univ. of Texas, Austin, TX (United States). Dept. of Physics
  2. Weizmann Inst. of Science, Rehovot (Israel). Dept. of Materials and Interfaces
  3. Univ. of Texas, Austin, TX (United States). Center for Computational Materials. Inst. for Computational Engineering and Sciences. Dept. of Physics. Dept. of Chemical Engineering
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465670
Alternate Identifier(s):
OSTI ID: 1330973
Grant/Contract Number:  
FG02-06ER46286
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; density functional theory; Stark effect; electric fields; convergences; electric dipole moments; boundary value problems; ground states; molecular dynamics; potential energy surfaces; wave functions

Citation Formats

Garrett, Benjamin F., Azuri, Ido, Kronik, Leeor, and Chelikowsky, James R. Real-space pseudopotential method for computing the vibrational Stark effect. United States: N. p., 2016. Web. doi:10.1063/1.4965918.
Copy to clipboard
Garrett, Benjamin F., Azuri, Ido, Kronik, Leeor, & Chelikowsky, James R. Real-space pseudopotential method for computing the vibrational Stark effect. United States. https://doi.org/10.1063/1.4965918
Copy to clipboard
Garrett, Benjamin F., Azuri, Ido, Kronik, Leeor, and Chelikowsky, James R. Fri . "Real-space pseudopotential method for computing the vibrational Stark effect". United States. https://doi.org/10.1063/1.4965918. https://www.osti.gov/servlets/purl/1465670.
Copy to clipboard
@article{osti_1465670,
title = {Real-space pseudopotential method for computing the vibrational Stark effect},
author = {Garrett, Benjamin F. and Azuri, Ido and Kronik, Leeor and Chelikowsky, James R.},
abstractNote = {The vibrational Stark shift is an important effect in determining the electrostatic environment for molecular or condensed matter systems. However, accurate ab initio calculations of the vibrational Stark effect are a technically demanding challenge. In this paper, we make use of density functional theory constructed on a real-space grid to expedite the computation of this effect. Our format is especially advantageous for the investigation of small molecules in finite fields as cluster boundary conditions eliminate spurious supercell interactions and allow for charged systems, while convergence is controlled by a single parameter, the grid spacing. The Stark tuning rate is highly sensitive to the interaction between anharmonicity in a vibrational mode and the applied field. To ensure this subtle interaction is fully captured, we apply three parallel approaches: a direct finite field, a perturbative method, and a molecular dynamics method. Finally, we illustrate this method by applying it to several small molecules containing C–O and C–N bonds and show that a consistent result can be obtained.},
doi = {10.1063/1.4965918},
journal = {Journal of Chemical Physics},
number = 17,
volume = 145,
place = {United States},
year = {Fri Nov 04 00:00:00 EDT 2016},
month = {Fri Nov 04 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.4965918
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Vibrational Stark Effect Probes for Nucleic Acids
journal, October 2007

  • Silverman, Lisa N.; Pitzer, Michael E.; Ankomah, Peter O.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 40
  • DOI: 10.1021/jp0750912

Vibrational Stark Effect of the Electric-Field Reporter 4-Mercaptobenzonitrile as a Tool for Investigating Electrostatics at Electrode/SAM/Solution Interfaces
journal, June 2012

  • Schkolnik, Gal; Salewski, Johannes; Millo, Diego
  • International Journal of Molecular Sciences, Vol. 13, Issue 6
  • DOI: 10.3390/ijms13067466

First-Principles Determination of the Soft Mode in Cubic ZrO 2
journal, May 1997

Vibrational Stark Effects on Carbonyl, Nitrile, and Nitrosyl Compounds Including Heme Ligands, CO, CN, and NO, Studied with Density Functional Theory
journal, May 2004

  • Dalosto, Sergio D.; Vanderkooi, Jane M.; Sharp, Kim A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 20
  • DOI: 10.1021/jp0310697

Ab initio molecular dynamics simulations using a Chebyshev-filtered subspace iteration technique
journal, August 2010

Highest electron affinity as a predictor of cluster anion structures
journal, September 2002

  • Kronik, Leeor; Fromherz, Roland; Ko, Eunjung
  • Nature Materials, Vol. 1, Issue 1
  • DOI: 10.1038/nmat704

Vibrational Stark Spectroscopy of NO Bound to Heme:  Effects of Protein Electrostatic Fields on the NO Stretch Frequency
journal, December 2000

  • Park, Eun Sun; Thomas, Melissa R.; Boxer, Steven G.
  • Journal of the American Chemical Society, Vol. 122, Issue 49
  • DOI: 10.1021/ja0014741

Vibrational Stark Spectroscopy in Proteins:  A Probe and Calibration for Electrostatic Fields
journal, November 1999

  • Park, Eun Sun; Andrews, Steven S.; Hu, Robert B.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 45
  • DOI: 10.1021/jp992329g

Real-space calculations of atomic and molecular polarizabilities using asymptotically correct exchange-correlation potentials
journal, July 2010

Vibrational Stark Spectroscopy 3. Accurate Benchmark ab Initio and Density Functional Calculations for CO and CN -
journal, December 1999

  • Reimers, Jeffrey R.; Hush, Noel S.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 49
  • DOI: 10.1021/jp992218h

A quantitative theory and computational approach for the vibrational Stark effect
journal, July 2003

  • Brewer, Scott H.; Franzen, Stefan
  • The Journal of Chemical Physics, Vol. 119, Issue 2
  • DOI: 10.1063/1.1578471

Vibrational Stark tuning rates from periodic DFT calculations: CO/Pt(111)
journal, February 2008

On quantal bound state solutions and potential energy surface fitting. A comparison of the finite element, Numerov-Cooley and finite difference methods
journal, November 1980

Some multistep methods for use in molecular dynamics calculations
journal, February 1976

Ab initio structures and polarizabilities of sodium clusters
journal, September 2001

  • Kronik, Leeor; Vasiliev, Igor; Jain, Manish
  • The Journal of Chemical Physics, Vol. 115, Issue 9
  • DOI: 10.1063/1.1390524

PARSEC – the pseudopotential algorithm for real-space electronic structure calculations: recent advances and novel applications to nano-structures
journal, April 2006

  • Kronik, Leeor; Makmal, Adi; Tiago, Murilo L.
  • physica status solidi (b), Vol. 243, Issue 5
  • DOI: 10.1002/pssb.200541463

Molecular dynamics with quantum forces: Vibrational spectra of localized systems
journal, May 1996

Phosphate Vibrations Probe Local Electric Fields and Hydration in Biomolecules
journal, August 2011

  • Levinson, Nicholas M.; Bolte, Erin E.; Miller, Carrie S.
  • Journal of the American Chemical Society, Vol. 133, Issue 34
  • DOI: 10.1021/ja2042589

The chemical bond in external electric fields: Energies, geometries, and vibrational Stark shifts of diatomic molecules
journal, October 2013

  • Sowlati-Hashjin, Shahin; Matta, Chérif F.
  • The Journal of Chemical Physics, Vol. 139, Issue 14
  • DOI: 10.1063/1.4820487

Ground State of the Electron Gas by a Stochastic Method
journal, August 1980

Vibrational Stark effect of adsorbates at electrochemical interfaces
journal, April 1996

Ab initio Calculations for the Polarizabilities of Small Semiconductor Clusters
journal, June 1997

Testing of Diatomic Potential‐Energy Functions by Numerical Methods
journal, October 1963

  • Cashion, J. K.
  • The Journal of Chemical Physics, Vol. 39, Issue 7
  • DOI: 10.1063/1.1734545

Nitrile Bonds as Infrared Probes of Electrostatics in Ribonuclease S
journal, October 2010

  • Fafarman, Aaron T.; Boxer, Steven G.
  • The Journal of Physical Chemistry B, Vol. 114, Issue 42
  • DOI: 10.1021/jp106406p

Efficient pseudopotentials for plane-wave calculations
journal, January 1991

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: