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

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]
  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:
Grant/Contract Number:
FG02-06ER46286
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)
Research Org:
Univ. of Texas, Austin, TX (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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
OSTI Identifier:
1465670
Alternate Identifier(s):
OSTI ID: 1330973

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., Web. doi:10.1063/1.4965918.
Garrett, Benjamin F., Azuri, Ido, Kronik, Leeor, & Chelikowsky, James R.. Real-space pseudopotential method for computing the vibrational Stark effect. United States. doi:10.1063/1.4965918.
Garrett, Benjamin F., Azuri, Ido, Kronik, Leeor, and Chelikowsky, James R.. 2016. "Real-space pseudopotential method for computing the vibrational Stark effect". United States. doi:10.1063/1.4965918. https://www.osti.gov/servlets/purl/1465670.
@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 = {2016},
month = {11}
}