First-order derivative couplings between excited states from adiabatic TDDFT response theory

• Published in: The Journal of chemical physics 2015-02, Vol.142 (6)
• Main Authors: Ou, Qi, Subotnik, Joseph E., Bellchambers, Gregory D., Furche, Filipp
• Format: Article
• Language: English
• Subjects: ADIABATIC APPROXIMATION; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; EQUATIONS; EXCITATION; EXCITED STATES; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; KERNELS; RESPONSE FUNCTIONS; TIME DEPENDENCE; WAVE FUNCTIONS
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4906941

We present a complete derivation of derivative couplings between excited states in the framework of adiabatic time-dependent density functional response theory. Explicit working equations are given and the resulting derivative couplings are compared with derivative couplings from a pseudo-wavefunction ansatz. For degenerate excited states, i.e., close to a conical intersection (CI), the two approaches are identical apart from an antisymmetric overlap term. However, if the difference between two excitation energies equals another excitation energy, the couplings from response theory exhibit an unphysical divergence. This spurious behavior is a result of the adiabatic or static kernel approximation of time-dependent density functional theory leading to an incorrect analytical structure of the quadratic response function. Numerical examples for couplings close to a CI and for well-separated electronic states are given.