Ames-2021 CO2 Dipole Moment Surface and IR Line Lists: Toward 0.1% Uncertainty for CO2 IR Intensities

Xinchuan Huang; David W Schwenke; Richard S Freedman; Timothy J Lee

doi:10.1021/acs.jpca.2c01291

Ames-2021 CO₂ Dipole Moment Surface and IR Line Lists: Toward 0.1% Uncertainty for CO₂ IR Intensities

J Phys Chem A. 2022 Sep 8;126(35):5940-5964. doi: 10.1021/acs.jpca.2c01291. Epub 2022 Aug 25.

Authors

Xinchuan Huang^{1

2}, David W Schwenke³, Richard S Freedman^{2

4}, Timothy J Lee⁴

Affiliations

¹ MS 245-6, Astrophysics Branch, Space Science and Astrobiology Division, NASA Ames Research Center, Moffett Field, California 94035, United States.
² SETI Institute, 339 Bernardo Avenue, Suite 200, Mountain View, California 94043, United States.
³ MS 258-2, NAS Facility, NASA Ames Research Center, Moffett Field, California 94035, United States.
⁴ MS 245-3, Planetary Systems Branch, Space Science and Astrobiology Division, NASA Ames Research Center, Moffett Field, California 94035, United States.

PMID: 36007245
DOI: 10.1021/acs.jpca.2c01291

Abstract

A highly accurate CO₂ ab initio dipole moment surface (DMS), Ames-2021, is reported along with ¹²C¹⁶O₂ infrared (IR) intensity comparisons approaching a 1-4‰ level of agreement and uncertainty. The Ames-2021 DMS was accurately fitted from CCSD(T) finite-field dipoles computed with the aug-cc-pVXZ (X = T, Q, 5) basis for C atom and the d-aug-cc-pVXZ (X = T, Q, 5) basis for O atoms, and extrapolated to the one particle basis set limit. Fitting σ_rms is 3.8 × 10^-7 au for 4443 geometries below 15 000 cm^-1. The corresponding IR intensity, S_Ames-2021, are computed using the Ames-2 potential energy surface (PES), which is the best PES available for CO₂. Compared to high accuracy IR studies for 2001i-00001 and 3001i-00001 bands, S_Ames-2021 matches NIST experiment-based intensities [S_NIST-HIT16 or S_HIT20] to -1.0 ± 1.3‰, or matches DLR experiment-based intensities [S_{DLR-HIT16/UCL/Ames}] to 1.9 ± 3.7‰. This indicates the systematic deviations and uncertainties have been significantly reduced in S_Ames-2021. The S_UCL2015 (or S_HITRAN2016) have larger deviations (vs S_DLR) and uncertainties (vs S_DLR, S_NIST) which are attributed to the less accurate Ames-1 PES adopted in UCL-296 line list calculation. The S_Ames-2021 intensity of ¹²C¹⁶O₂ and ¹³C¹⁶O₂ is utilized to derive new absolute ¹³C/¹²C ratios for Vienna PeeDee Belemnite (VPDB) with uncertainty reduced by ¹/₃ or ²/₃. Further evaluation of S_Ames-2021 intensities are carried out on those CO₂ bands discussed in the HITRAN2020 update paper. Consistent improvements and better accuracies are found in band-by-band analysis, except for those bands strongly affected by Coriolis couplings, or very weak bands measured with relatively larger experimental uncertainties. The Ames-2021 296 K IR line lists are generated for 13 CO₂ isotopologues, with 18 000 cm^-1 and S_{296 K} > 1 × 10^-31 cm/molecule cutoff and then combined with CDSD line positions (except ¹⁴C¹⁶O₂). The Ames-2021 DMS and 296 K IR line lists represent a major improvement over previous CO₂ theoretical IR intensity studies, including Ames-2016, UCL-296, and recent UCL DMS 2021 update. A real 1 permille level of agreement and uncertainty will definitely require both more accurate PES and more accurate DMS.