Vibrational and Rovibrational Spectroscopic Data for the Ground and First-Excited States of Phosgene (COCl2), Formic Acid (HCOOH), and Chloroformic Acid (ClCOOH).

Abstract

While "black box" quantum chemical computations for the determination of rovibronic spectral data are not quite at hand, the present work utilizes the titular molecules to showcase how excited-state quantum chemical methods can be conjoined to quartic force field (QFF) anharmonic rovibrational treatments to provide novel and useful predictions for such data. This work employs hybrid QFFs with explicitly correlated coupled cluster theory along with the equation-of-motion formalism to generate harmonic force constants and time-dependent density functional theory (TD-DFT) to produce anharmonic force constants for the generation of electronically excited-state rovibrational spectral data, in effect, rovibronic spectral data. Specific spectroscopic results from this work show that the fundamental C═O stretch in phosgene as well as in cis- and trans-formic acid drop from the region of around 1800 cm-1 to close to 1100 cm-1 or less in the first excited states of each molecule. While such is expected for these n → π* excitations, this work provides quantitative predictions for these fundamental vibrational frequencies. The most notable theoretical result is that the TD-DFT-based QFFs can experience unexpected failures, and their inclusion in excited-state hybrid QFFs should require at least two functionals to be employed. The computation of DFT QFFs is relatively fast, and such a "doubling up" of the QFFs will not greatly increase the computational time.