Conformational potential energy surfaces and cationic structure of 3,4-dihydro-2H-pyran by VUV-MATI spectroscopy and Franck–Condon fitting

Abstract

Ring conformations of 3,4-dihydro-2H-pyran (34DHP) have attracted considerable interest owing to their structural similarity to cyclohexene, an important molecule in stereochemistry. In this study, we investigated the conformational interconversion of 34DHP in both the neutral (S₀) and the cationic (D₀) ground states. High-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy was utilized to obtain information regarding the adiabatic ionic transition between the S₀ and the D₀ states. Based on the 0–0 band in the VUV-MATI spectrum supported by the VUV-photoionization efficiency curve, the adiabatic ionization energy of 34DHP was accurately determined to be 8.3355 ± 0.0005 eV (67 230 ± 4 cm⁻¹). To identify the conformer corresponding to this measured value, two-dimensional potential energy surfaces (2D PESs) associated with conformational interconversion in the S₀ and the D₀ states were constructed at the B3LYP/aug-cc-pVTZ level. It was revealed that in the S₀ state, the twisted conformers undergo interconversion through the asymmetric bent conformation on the pseudorotational pathway, whereas in the D₀ state, the half-bent conformers directly undergo interconversion via the planar conformation at the saddle point of 2D PES. The change in the conformational interconversion pathway upon ionization is attributed to electron removal from the highest occupied molecular orbital, which consists of a π orbital in the 2C–3C double bond interacting with a nonbonding orbital in the oxygen atom of 34DHP. Then, vibrational assignment of the observed spectrum could be achieved through Franck–Condon fitting for ionic transitions between the neutral twisted and the cationic half-bent conformers. The strong promotion of the ring bending and the 1O–2C–3C asymmetric stretching modes in the adiabatic ionic transitions confirmed the determined cationic structure of 34DHP.