(T)+EOM Quartic Force Fields for Theoretical Vibrational Spectroscopy of Electronically Excited States.

Abstract

(T)+EOM quartic force fields (QFFs) are proposed for ab initio rovibrational properties of electronically excited states of small molecules. The (T)+EOM method is a simple treatment of the potential surface of the excited state using a composite energy from the CCSD(T) energy for the ground-state configuration and the EOM-CCSD excitation energy for the target state. The method is benchmarked with two open-shell species, HOO and HNF, and two closed-shell species, HNO and HCF. A (T)+EOM QFF with a complete basis set extrapolation (C) and corrections for core correlation (cC) and scalar relativity (R), dubbed (T)+EOM/CcCR, achieves a mean absolute error (MAE) as low as 1.6 cm-1 for the à 2A' state of HOO versus an established benchmark QFF with CCSD(T)-F12b/cc-pVTZ-F12 (F12-TZ) for this variationally accessible electronically excited state. The MAE for anharmonic frequencies for (T)+EOM/CcCR versus F12-TZ for HNF is 7.5 cm-1. The closed-shell species are compared directly with the experiment, where a simpler (T)+EOM QFF using the aug-cc-pVTZ basis set compares more favorably than the more costly (T)+EOM/CcCR, suggesting a possible influence of decreasing accuracy with basis set size. Scans along internal coordinates are also provided which show reasonable modeling of the potential surface by (T)+EOM compared to benchmark QFFs computed for variationally accessible electronic states. The agreement between (T)+EOM/CcCR with F12-TZ and CcCR benchmarks is also shown to be quite accurate for rotational constants and geometries, with an MAE of 0.008 MHz for the rotational constants of (T)+EOM/CcCR versus CcCR for à 2A' HOO and agreement within 0.003 Šfor bond lengths.