Chemical Interpretation of Time-Dependent Coupled-Cluster Theory.

While providing a highly accurate framework for simulating laser-induced many-electron dynamics in atoms and molecules, including linear and nonlinear steady-state and transient absorption spectra, time-dependent coupled-cluster theory does not offer a straightforward interpretation in chemical terms. This should be contrasted with conventional time-independent equation-of-motion coupled-cluster or frequency-dependent response models where a simple eigenvector analysis readily reveals the dominant orbital-excitation character of individual excited states. We fill this gap by expanding the left and right coupled-cluster functions in a Slater-determinant basis, thus allowing for a time-dependent generalization of configuration weights that can be used to track populations throughout a simulation. The same expansions are used to decompose the time-dependent electric-dipole moment and autocorrelation function, providing a computationally straightforward approach to the assignment of absorption peaks to orbital transitions for single-reference systems. At the time-dependent coupled-cluster singles-and-doubles level of theory, we demonstrate the power of the proposed methodology by assigning valence lines in the linear absorption spectra of four ten-electron molecules (HF, H2O, NH3, and CH4) with different point-group symmetries, validating the assignment by comparison with equation-of-motion coupled-cluster singles-and-doubles theory. In addition, core-level excitations are assigned for HF, H2O, and NH3. Finally, the usefulness of time-dependent configuration weights is illustrated by applications to an impulsive stimulated X-ray Raman scattering process in the Ne atom and to a transient pump-probe spectrum of the HF molecule.