TY - JOUR
T1 - Calculated molecular properties and microwave spectrum analysis for formamidinium formate
AU - Jiménez Hoyos, Carlos A.
AU - Zhou, Zunwu
AU - Kukolich, Stephen G.
N1 - Funding Information:
This material is based upon work supported by the National Science Foundation, United States under Grant No. CHE-1057796 at the University of Arizona . CAJH is grateful for support from a start-up package from Wesleyan University. We are very grateful to UITS-HPC computing facilities for the computing time provided on the Ocelote system. This material is based, in part, upon High Performance Computing (HPC) resources supported by the University of Arizona TRIF, UITS, and Research, Innovation, and Impact (RII) and maintained by the UArizona Research Technologies department. We thank Jimmy Ferng for assistance with the calculations, which was made possible through University of Arizona Research Technologies Collaborative Support program.
Funding Information:
This material is based upon work supported by the National Science Foundation, United States under Grant No. CHE-1057796 at the University of Arizona. CAJH is grateful for support from a start-up package from Wesleyan University. We are very grateful to UITS-HPC computing facilities for the computing time provided on the Ocelote system. This material is based, in part, upon High Performance Computing (HPC) resources supported by the University of Arizona TRIF, UITS, and Research, Innovation, and Impact (RII) and maintained by the UArizona Research Technologies department. We thank Jimmy Ferng for assistance with the calculations, which was made possible through University of Arizona Research Technologies Collaborative Support program. We thank Michael Palmer, University of Edinburgh for earlier calculations on this complex.
Publisher Copyright:
© 2020 Elsevier Inc.
PY - 2020/7/1
Y1 - 2020/7/1
N2 - Formamidinium formate occurs in the gas phase as a doubly hydrogen-bonded dimer. New high-level calculations on formamidinium formate using various methods and basis sets are described. The calculated rotational constants and quadrupole coupling constants given here are reasonably consistent between the different methods and in reasonably good agreement with values obtained from the new analysis of the microwave data. In the revised fit 38 measured transitions are fit with a standard deviation of 30 kHz. The revised rotational, centrifugal distortion and quadrupole coupling constants determined from the spectra have values: A = 5890.39(8), B = 2148.731(1), C = 1575.0958(8), 1.5 χaa (N1) = 2.254(24), 0.25(χbb - χcc)(N1) = 1.747(12), 1.5χaa (N2) = -3.134(29), 0.25(χbb - χcc)(N2) = 0.553(10) MHz. The calculated rotational constants which agree best with experiment are from an M11 /def2-QZVPP calculation: A = 5785.29, B = 2143.25and C = 1563.88 MHz. The calculated quadrupole coupling constants which agree best with experiment are from a PBE0 aug-cc-pVQZ (uncontracted) calculation: 1.5 χaa (N1) = 1.78, 0.25(χbb - χcc)(N1) = 1.49, 1.5χaa (N2) = -3.41), 0.25(χbb - χcc)(N2) = 0.51 MHz. The calculated rotational constants agree within 2%, and quadrupole coupling constants within 11% or better with the experimental values.
AB - Formamidinium formate occurs in the gas phase as a doubly hydrogen-bonded dimer. New high-level calculations on formamidinium formate using various methods and basis sets are described. The calculated rotational constants and quadrupole coupling constants given here are reasonably consistent between the different methods and in reasonably good agreement with values obtained from the new analysis of the microwave data. In the revised fit 38 measured transitions are fit with a standard deviation of 30 kHz. The revised rotational, centrifugal distortion and quadrupole coupling constants determined from the spectra have values: A = 5890.39(8), B = 2148.731(1), C = 1575.0958(8), 1.5 χaa (N1) = 2.254(24), 0.25(χbb - χcc)(N1) = 1.747(12), 1.5χaa (N2) = -3.134(29), 0.25(χbb - χcc)(N2) = 0.553(10) MHz. The calculated rotational constants which agree best with experiment are from an M11 /def2-QZVPP calculation: A = 5785.29, B = 2143.25and C = 1563.88 MHz. The calculated quadrupole coupling constants which agree best with experiment are from a PBE0 aug-cc-pVQZ (uncontracted) calculation: 1.5 χaa (N1) = 1.78, 0.25(χbb - χcc)(N1) = 1.49, 1.5χaa (N2) = -3.41), 0.25(χbb - χcc)(N2) = 0.51 MHz. The calculated rotational constants agree within 2%, and quadrupole coupling constants within 11% or better with the experimental values.
KW - Calculations of molecular properties
KW - Hydrogen bonding
KW - Microwave spectroscopy
KW - Quadrupole hyperfine structure
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U2 - 10.1016/j.jms.2020.111331
DO - 10.1016/j.jms.2020.111331
M3 - Article
AN - SCOPUS:85088831100
VL - 372
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
SN - 0022-2852
M1 - 111331
ER -