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Updated: Dec 15, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Frequency and Time Domain Nuclear-Electronic Orbital Equation-of-Motion Coupled Cluster Methods: Combination Bands
Fabijan Pavošević1, Zhen Tao1, Tanner Culpitt1
1Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520, United States.
Abstract:
The accurate description of excited vibronic states is important for modeling a wide range of photoinduced processes. The nuclear-electronic orbital (NEO) approach, which treats specified protons on the same level as the electrons, can describe excited electronic-protonic states. Herein the multicomponent equation-of-motion coupled cluster with singles and doubles (NEO-EOM-CCSD) method and its time-domain counterpart, TD-NEO-EOM-CCSD, are developed and implemented. The application of these methods to the HCN molecule highlights their capabilities. These methods predict qualitatively reasonable energies and intensities for a combination band corresponding to simultaneous excitation of two vibrational modes, as well as an overtone. These methods also describe states with double excitation character, such as excited electronic-protonic states corresponding to the simultaneous excitation of an electron and a proton. The ability of the NEO-EOM-CCSD method and its time-dependent counterpart to describe combination bands, overtones, and double excitations will enable a wide range of photochemical applications.
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