Spectra represent fingerprints of molecules, which contain unique information about their properties. Through analyzing the spectral data, one can reveal the molecules' energy level alignments, identify their species and geometric structures, and explore relevant chemical processes and microscopic mechanisms. Currently, spectroscopy is one of the main means for human beings to enter the mysterious world of molecules and hear their stories. However, interpreting molecular spectra is not a straightforward process, because the occurrence of spectra involves complex interactions between molecules and external stimuli. Theoretical simulations based on quantum chemistry play an indispensable role in this regard, which makes developing and applying related computational software become very important.
This thesis focuses on the theoretical simulations of two types of molecular spectra, namely the vibrationally resolved optical spectra and the inelastic electron tunneling spectra (IETS). The former involves the transitions of electrons between a molecule's ground state and its excited states with the involvement of molecular vibrations, and the latter comes from the excitations of a molecule's vibrational states within its electronic ground state by inelastic tunneling electrons across a molecular junction.
By performing time-dependent density functional theory calculations as well as applying the DynaVib code, I have systematically investigated the optical absorption properties of two types of functional molecules, i.e., naphthalenediimide cyclophane (NDIC) derivatives and fused porphyrin derivatives, which have been proposed as building blocks for future single-molecule optoelectronic devices. Based on the Franck-Condon (FC) principle, the simulations well explain the energy shifts induced by chemical substitutions in the first intense absorption bands of the three NDIC derivatives, and nicely reproduce the vibrational features of their first two bands. Furthermore, by using three different exchange-correlation functionals (i.e., the conventional functional B3LYP and two long-range corrected functionals CAM-B3LYP and wB97XD), it is found that long-range corrections are very important for the description of the spectral features owing to the strong charge transfer in the related excited states. By taking into account both the FC and the non-FC Herzberg-Teller (HT) contributions, the experimentally measured electroluminescence spectrum of a single fused 5,15-(diphenyl)-10,20-(dibromo)porphyrin (fused-H2P) molecule is nicely reproduced by the simulations. It is found that the FC contribution also dominates the emission of the molecule, while the HT terms mainly contribute to the low-energy tail of the spectrum. The vibrational fine structures as observed in the experiments are unambiguously assigned based on the simulation results.
In terms of the development of computational software, I have developed a Windows version for the QCME package - an efficient package to perform first principles calculations of electron transport through molecules such as simulating the IETS. The implementation has been achieved by using the C# language and the Windows Presentation Foundation (WPF) user interface framework. The Windows version of QCME exhibits compatibility, stability, scalability, and strong operability. It has a beautiful interface, is easy to learn and to use, and has improved human-computer interactions. Such an approach of the implementation can be also extended to other quantum chemistry packages.