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Title: Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules

Abstract

We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An application is illustrated by calculating the infrared vibrational dipole transition spectrum of CH{sub 4} based on the ab initio T8 potential energy surface of Schwenke and Partridge [Spectrochimica Acta, Part A 57, 887 (2001)] and the low-order truncated ab initio dipole moment surfaces of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.

Authors:
 [1]
  1. Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)
Publication Date:
OSTI Identifier:
22416034
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALGORITHMS; ANGULAR MOMENTUM; COMPARATIVE EVALUATIONS; DIPOLE MOMENTS; DIPOLES; HAMILTONIANS; INFRARED SPECTRA; LAYERS; METHANE; MOLECULES; POLARIZABILITY; POTENTIAL ENERGY; RESIDUES; SURFACES; WAVE FUNCTIONS

Citation Formats

Yu, Hua-Gen. Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules. United States: N. p., 2015. Web. doi:10.1063/1.4906492.
Yu, Hua-Gen. Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules. United States. https://doi.org/10.1063/1.4906492
Yu, Hua-Gen. 2015. "Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules". United States. https://doi.org/10.1063/1.4906492.
@article{osti_22416034,
title = {Multi-layer Lanczos iteration approach to calculations of vibrational energies and dipole transition intensities for polyatomic molecules},
author = {Yu, Hua-Gen},
abstractNote = {We report a rigorous full dimensional quantum dynamics algorithm, the multi-layer Lanczos method, for computing vibrational energies and dipole transition intensities of polyatomic molecules without any dynamics approximation. The multi-layer Lanczos method is developed by using a few advanced techniques including the guided spectral transform Lanczos method, multi-layer Lanczos iteration approach, recursive residue generation method, and dipole-wavefunction contraction. The quantum molecular Hamiltonian at the total angular momentum J = 0 is represented in a set of orthogonal polyspherical coordinates so that the large amplitude motions of vibrations are naturally described. In particular, the algorithm is general and problem-independent. An application is illustrated by calculating the infrared vibrational dipole transition spectrum of CH{sub 4} based on the ab initio T8 potential energy surface of Schwenke and Partridge [Spectrochimica Acta, Part A 57, 887 (2001)] and the low-order truncated ab initio dipole moment surfaces of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.},
doi = {10.1063/1.4906492},
url = {https://www.osti.gov/biblio/22416034}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 142,
place = {United States},
year = {Wed Jan 28 00:00:00 EST 2015},
month = {Wed Jan 28 00:00:00 EST 2015}
}

Works referencing / citing this record:

A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3
journal, June 2017


Infrared vibrational spectra of CH3+ and its deuterated isotopologues
journal, September 2019