The overarching goal of this work is to systematically investigate the statistical distributions of fundamental molecular quantum mechanical properties that arise as a consequence of having a distribution of conformations and extract statistical inferences that are chemically relevant. Noise in chemical environment appears as a consequence of non-zero temperatures and presence of surround media such as solvents. In this work, we introduce the effective stochastic potential (ESP) method for calculation of excited state properties of solvated chemical systems at non-zero temperatures. The central idea of the ESP method is to provide a statistical description of the surrounding chemical environment by a stochastic representation of fluctuations in the environment. The excitation energies are obtained by combining the ESP method with CIS and linear-response TDDFT methods. In the first step, the single-particle energies and states are obtained by performing ESP-HF and ESP-DFT calculations. In the second step, the ESP single-particle states and energies are used for the construction of the response matrices (known as A and B matrices) in the ESP-CIS and ESP-LR-TDDFT formulations. The ESP method has also been combined with 1-particle Green’s function method (ESP-GF) for calculation of quasiparticle energies and quasiparticle gap. This presentation will focus on the development of the ESP-CIS, ESP-LR-TDDFT, and ESP-GF methods for obtaining distributions of ionization potentials, electron affinities, excitation energies, and oscillator strengths in chemical systems at non-zero temperatures.

Obtaining a statistical description of excited state properties in noisy chemical environments

256th National Meeting (2018)

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