Fulminic acid: a quasibent spectacle

Abstract

Fulminic acid (HCNO) played a critical role in the early development of organic chemistry, and chemists have sought to discern the structure and characteristics of this molecule and its isomers for over 200 years. The mercurial nature of the extremely flat H-C-N bending potential of fulminic acid, with a nearly vanishing harmonic vibrational frequency at linearity, remains enigmatic and refractory to electronic structure theory, as dramatic variation with both orbital basis set and electron correlation method is witnessed. To solve this problem using rigorous electronic wavefunction methods, we have employed focal point analyses (FPA) to ascertain the ab initio limit of optimized linear and bent geometries, corresponding vibrational frequencies, and the HCN + O(³P) → HCNO reaction energy. Electron correlation treatments as extensive as CCSDT(Q), CCSDTQ(P), and even CCSDTQP(H) were employed, and complete basis set (CBS) extrapolations were performed using the cc-pCVXZ (X = 4-6) basis sets. Core electron correlation, scalar relativistic effects (MVD1), and diagonal Born-Oppenheimer corrections (DBOC) were all included and found to contribute significantly in determining whether vibrationless HCNO is linear or bent. At the all-electron (AE) CCSD(T)/CBS level, HCNO is a linear molecule with ω₅(H-C-N bend) = 120 cm^-1. However, composite AE-CCSDT(Q)/CBS computations give an imaginary frequency (51i cm^-1) at the linear optimized geometry, leading to an equilibrium structure with an H-C-N angle of 173.9°. Finally, at the AE-CCSDTQ(P)/CBS level, HCNO is once again linear with ω₅ = 45 cm^-1, and inclusion of both MVD1 and DBOC effects yields ω₅ = 32 cm^-1. A host of other topics has also been investigated for fulminic acid, including the dependence of r_e and ω_i predictions on a variety of CBS extrapolation formulas, the question of multireference character, the N-O bond energy and enthalpy of formation, and issues that give rise to the quasibent appellation.