Energy Functional and Hamiltonians

We start out with a section on the energy functionals and Hamiltonians that are relevant for molecular systems interacting with a structured environment. We continue with a section that briefly describes the correlated electron structure method, the multiconfigurational self-consistent field (MCSCF) electronic structure method. In the following section we cover the procedure for obtaining the correlated MCSCF response equations for the two different models describing molecules in structured environments. The final sections provide a brief overview of the results obtained using the two methods and a conclusion. 

In order to investigate the energies and molecular properties of molecules interacting with aerosol particles, it is crucial to establish the Hamiltonians and the energy functionals for the two structural environment methods. The basic principle for both structural environment methods is the same and it is one that has been utilized successfully within quantum chemistry [2-33] and molecular reaction dynamics [19,68-71,96], we divide a large system into two subsystems. The focus is 

For both methods, we describe the interactions between the quantum subsystem and the classical subsystem as interactions between charges and/or induced charges/dipoles and a van der Waals term [2-18]. The coupling between the quantum subsystem and the classical subsystem is introduced into the quantum mechanical Hamiltonian by finding effective interaction operators for the interactions between the two subsystems. This provides an effective Schrodinger equation for determining the MCSCF electronic wave function of the molecular system exposed to a classical environment, a structured environment, such as an aerosol particle. 

1 A structured environment model based on the heterogeneous dielectric media method 

Thereby, we have defined a heterogeneous dielectric model with a hemisperical cavity, C, having a radius of R and positioned such that the cavity C is on the surface of Sm and embedded in S . The volume of the cavity C is 

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This contribution starts out with a section describing how to obtain the energy functionals and Hamiltonians when a molecular system is interacting with a structured... 

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