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Title: Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates

Abstract

This article presents a general computational approach for efficient simulations of anharmonic vibrational spectra in chemical systems. An automated local-mode vibrational approach is presented, which borrows techniques from localized molecular orbitals in electronic structure theory. This approach generates spatially localized vibrational modes, in contrast to the delocalization exhibited by canonical normal modes. The method is rigorously tested across a series of chemical systems, ranging from small molecules to large water clusters and a protonated dipeptide. It is interfaced with exact, grid-based approaches, as well as vibrational self-consistent field methods. Most significantly, this new set of reference coordinates exhibits a well-behaved spatial decay of mode couplings, which allows for a systematic, a priori truncation of mode couplings and increased computational efficiency. Convergence can typically be reached by including modes within only about 4 Å. The local nature of this truncation suggests particular promise for the ab initio simulation of anharmonic vibrational motion in large systems, where connection to experimental spectra is currently most challenging.

Authors:
;  [1]
  1. Department of Chemistry and Henry Eyring Center for Theoretical Chemistry, University of Utah, Salt Lake City, Utah 84112 (United States)
Publication Date:
OSTI Identifier:
22308359
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COUPLINGS; EFFICIENCY; ELECTRONIC STRUCTURE; INTERFACES; MOLECULES; SELF-CONSISTENT FIELD; SIMULATION; SPECTRA; SPECTROSCOPY; WATER

Citation Formats

Cheng, Xiaolu, and Steele, Ryan P., E-mail: ryan.steele@utah.edu. Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates. United States: N. p., 2014. Web. doi:10.1063/1.4894507.
Cheng, Xiaolu, & Steele, Ryan P., E-mail: ryan.steele@utah.edu. Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates. United States. doi:10.1063/1.4894507.
Cheng, Xiaolu, and Steele, Ryan P., E-mail: ryan.steele@utah.edu. 2014. "Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates". United States. doi:10.1063/1.4894507.
@article{osti_22308359,
title = {Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates},
author = {Cheng, Xiaolu and Steele, Ryan P., E-mail: ryan.steele@utah.edu},
abstractNote = {This article presents a general computational approach for efficient simulations of anharmonic vibrational spectra in chemical systems. An automated local-mode vibrational approach is presented, which borrows techniques from localized molecular orbitals in electronic structure theory. This approach generates spatially localized vibrational modes, in contrast to the delocalization exhibited by canonical normal modes. The method is rigorously tested across a series of chemical systems, ranging from small molecules to large water clusters and a protonated dipeptide. It is interfaced with exact, grid-based approaches, as well as vibrational self-consistent field methods. Most significantly, this new set of reference coordinates exhibits a well-behaved spatial decay of mode couplings, which allows for a systematic, a priori truncation of mode couplings and increased computational efficiency. Convergence can typically be reached by including modes within only about 4 Å. The local nature of this truncation suggests particular promise for the ab initio simulation of anharmonic vibrational motion in large systems, where connection to experimental spectra is currently most challenging.},
doi = {10.1063/1.4894507},
journal = {Journal of Chemical Physics},
number = 10,
volume = 141,
place = {United States},
year = 2014,
month = 9
}
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