Real-space pseudopotential method for computing the vibrational Stark effect

Benjamin F. Garrett, Ido Azuri, Leeor Kronik, James R. Chelikowsky

Research output: Contribution to journalArticlepeer-review


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. 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. 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.

Original languageEnglish
Article number174111
Number of pages6
JournalJournal of Chemical Physics
Issue number17
StatePublished - 7 Nov 2016

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Real-space pseudopotential method for computing the vibrational Stark effect'. Together they form a unique fingerprint.

Cite this