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Title: Convergent Concordant Mode Approach for Molecular Vibrations: CMA-2

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. University of Georgia, Athens, GA (United States); Indiana Wesleyan University, Marion, IN (United States)
  2. University of Georgia, Athens, GA (United States)
  3. University of Georgia, Athens, GA (United States); Allen Heritage Foundation, Dickson, TN (United States)
+ Show Author Affiliations

The concordant mode approach (CMA) is a promising new scheme for dramatically increasing the system size and level of theory achievable in quantum chemical computations of molecular vibrational frequencies. Here, we achieve advances in the CMA hierarchy by computations targeting CCSD(T)/cc-pVTZ (coupled cluster singles and doubles with perturbative triples using a correlation-consistent polarized-valence triple-ζ basis set) benchmarks within the G2 molecular test set, executing a statistical analysis for 1501 frequencies from 111 compounds and then separately solving the refractory case of pyridine. First, MP2/cc-pVTZ (second-order Møller–Plesset perturbation theory with the same basis set) proves to be an excellent and preferred choice for generating the underlying (Level B) normal modes of the CMA scheme. Utilizing this Level B within the CMA-0A method reproduces the 1501 benchmark frequencies with a mean absolute error (MAE) of only 0.11 cm–1 and an attendant standard deviation of 0.49 cm–1. Second, a convergent CMA-2 method is constituted that allows efficient computation of higher level (Level A) frequencies to any reasonable accuracy threshold by using only Hartree–Fock (HF) and MP2 or density functional theory (DFT) data to generate ξ parameters, which select the sparse off-diagonal force field elements for explicit evaluation at Level A. When Level B = MP2/cc-pVTZ, a cutoff of ξ = 0.02 provides an average maximum absolute error per molecule of only 0.17 cm–1 by incurring merely a 33% increase in average cost over CMA-0A. This CMA-2 method also eradicates the 4 problematic CMA-0A outliers of pyridine with even less effort (ξ = 0.04, 22% increase). Finally, the newly developed CMA procedures are shown to be highly successful when applied to 1-(1H-pyrrol-3-yl)ethanol, a new test molecule with diverse types of vibration.

Research Organization:
University of Georgia, Athens, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018412
OSTI ID:
2481385
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 24 Vol. 20; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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