Adiabatic Excited-State Molecular Dynamics with an Explicit Solvent: NEXMD-SANDER Implementation.

ABSTRACT

We present a method to link the Nonadiabatic EXcited-state Molecular Dynamics (NEXMD) package to the SANDER package supplied by AMBERTOOLS to provide excited-state adiabatic quantum mechanics/molecular mechanics (QM/MM) simulations. NEXMD is a computational package particularly developed to perform simulations of the photoexcitation and subsequent nonadiabatic electronic and vibrational energy relaxation in large multichromophoric conjugated molecules involving several coupled electronic excited states. The NEXMD-SANDER exchange has been optimized in order to achieve excited-state adiabatic dynamics simulations of large conjugated materials in a QM/MM environment, such as an explicit solvent. Dynamics of a substituted polyphenylene vinylene oligomer (PPV3-NO2) in vacuum and different explicit solvents has been used as a test case by performing comparative analysis of changes in its optical spectrum, state-dependent conformational changes, and quantum bond orderings. The method has been tested and compared with respect to previous implicit solvent implementations. Also, the impact on the expansion of the QM region by including a variable number of solvent molecules has been analyzed. Altogether, these results encourage future implementations of NEXMD simulations using the same combination of methods.