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Current simulations of ultraviolet-visible absorption lineshapes, anddynamics of condensed phase systems, largely adopt a harmonic description tomodel vibrations. Often, this involves a model of displaced harmonicoscillators that have the same curvature. Although convenient, for manyrealistic molecular systems this approximation no longer suffices. We elucidatenon-standard harmonic, and anharmonic effects, on linear absorption anddynamics using a stochastic Schr\"{o}dinger equation approach to account forthe environment. Firstly, a harmonic oscillator model with ground and excitedpotentials that differ in curvature is utilised. Using this model, it is shownthat curvature difference gives rise to an additional sub-structure in thevibronic progression of absorption spectra. This effect is explained, andsubsequently quantified, via a derived expression for the Franck-Condoncoefficients. Subsequently, anharmonic features in dissipative systems arestudied, using a Morse potential, and parameters that correspond to thediatomic molecule $H_{2}$ for differing displacements and environmentinteraction. Lastly using a model potential, the population dynamics andabsorption spectra for the stiff-stilbene photoswitch is presented and featuresare explained by a combination of curvature difference and anharmonicity in theform of potential energy barriers on the excited potential.

Quantum dissipative systems beyond the standard harmonic model: features of linear absorption and dynamics