Coupled Cluster Characterization of 1‑, 2‑, and 3‑Pyrrolyl: Parameters for Vibrational and Rotational Spectroscopy

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-02, Vol.125 (5), p.1257-1268
• Main Authors: Johansen, Sommer L, Xu, Zhongxing, Westerfield, J. H, Wannenmacher, Anna C, Crabtree, Kyle N
• Format: Article
• Language: English
• Subjects: A: Aerosols; Environmental and Atmospheric Chemistry; Astrochemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.0c09833

Pyrrolyl (C4H4N) is a nitrogen-containing aromatic radical that is a derivative of pyrrole (C4H5N) and is an important intermediate in the combustion of biomass. It is also relevant for chemistry in Titan’s atmosphere and may be present in the interstellar medium. The lowest-energy isomer, 1-pyrrolyl, has been involved in many experimental and theoretical studies of the N–H photodissociation of pyrrole, yet it has only been directly spectroscopically detected via electron paramagnetic resonance and through the photoelectron spectrum of the pyrrolide anion, yielding three vibrational frequencies. No direct measurements of 2- or 3-pyrrolyl have been made, and little information is known from theoretical calculations beyond their relative energies. Here, we present an ab initio quantum chemical characterization of the three pyrrolyl isomers at the CCSD­(T) level of theory in their ground electronic states, with an emphasis on spectroscopic parameters relevant for vibrational and rotational spectroscopy. Equilibrium geometries were optimized at the CCSD­(T)/cc-pwCVTZ level of theory, and the quadratic, cubic, and partial quartic force constants were evaluated at CCSD­(T)/ANO0 for analysis using second-order vibrational perturbation theory to obtain harmonic and anharmonic vibrational frequencies. In addition, zero-point-corrected rotational constants, electronic spin–rotation tensors, and nuclear hyperfine tensors are calculated for rotational spectroscopy. Our computed structures and energies agree well with earlier density functional theory calculations, and spectroscopic parameters for 1-pyrrolyl are compared with the limited existing experimental data. Finally, we discuss strategies for detecting these radicals using rotational and vibrational spectroscopy on the basis of the calculated spectroscopic constants.