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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4906492· OSTI ID:1182509
 [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
+ Show Author Affiliations

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 CH₄ based on the ab initio T8 potential energy surface of Schwenke and Partridge and the low-order truncated ab initio dipole moment surfaces of Yurchenko and co-workers. A comparison with experiments is made. The algorithm is also applicable for Raman polarizability active spectra.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704; AC02-98CH10886
OSTI ID:
1182509
Alternate ID(s):
OSTI ID: 1228133
Report Number(s):
BNL-107475-2015-JA; JCPSA6; R&D Project: CO006; KC0301020; TRN: US1500507
Journal Information:
Journal of Chemical Physics, Vol. 142, Issue 4; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

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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

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Eigenvalues
Wave functions
Lanczos method
Molecular spectra
dipole transition intensities
polyatomic molecules