Excited states state-specific methods

The state-specific method solves the nonlinear Schrodinger equation for the state of interest (ground and excited state) usually within a multirefence approach (Cl, MCSCF or CASSCF descriptions), and it postulates that the transition energies are differences between the corresponding values of the free energy functional, the basic energetic quantity of the QM continuum models. The nonlinear character of the reaction potential requires the introduction in the SS approaches of an iteration procedure not present in parallel calculations on isolated systems. 

At a given computational level, the solvent relaxation contribution to the excitation energy may be approximated by using two basically different methods, the state-specific method (SS) and the linear response method (LR), depending on the QM methodology used. This directly involves the problem of extending the PCM basic model to a QM description proper for excited states. 

Ah initio quantum chemical calculations are primarily used to describe the electronic character of individual molecules in the gas phase. Quantum chemical methods can vary widely in their accuracy, depending on the specific approximations taken. Those most applicable to the study of ionic liquids are medium level methods such as DFT and MP2 [20]. Hartree-Fock(HF) level calculations may be carried out as a starting point or to obtain geometries but should be followed by calculations that include some level of electronic correlation. Higher level methods such as Coupled Cluster methods (ie CCSD(T)) are only just accessible, and will not be routine. They do however allow for an estimation of effects hard to recover with the lower level DFT and MP2 methods, such as dispersion, more dynamic correlation, and an estimation of other neglected effects (such as the stabilization afforded by mixing in excited electronic states). The method employed (HF< DFT < MP2 < CCSD(T)) and sophistication of the basis set used are typically used to indicate the quality of an ab initio quantum chemical calculation. 

This is an introduction to the techniques used for the calculation of electronic excited states of molecules (sometimes called eximers). Specifically, these are methods for obtaining wave functions for the excited states of a molecule from which energies and other molecular properties can be calculated. These calculations are an important tool for the analysis of spectroscopy, reaction mechanisms, and other excited-state phenomena. 

So far everything is exact. A complete manifold of excitation operators, however, means that all excited states are considered, i.e. a full Cl approach. Approximate versions of propagator methods may be generated by restricting the excitation level, i.e. tmncating h. A complete specification furthermore requires a selection of the reference, normally taken as either an HF or MCSCF wave function. 

Other methods of excitation are effective or necessary for certain gain media. For example, certain energetic chemical reactions produce molecules in excited states. These excited molecules may then comprise the upper laser level of an inverted-population system. A specific example is the hydrogen fluoride "chemical laser" wherein excitation is provided by the reaction of hydrogen gas with atomic fluorine. Another method of excitation is simply the passage of an electric current through a semiconductor device. This serves as the exciter for diode lasers. 

Abstract. The development of modern spectroscopic techniques and efficient computational methods have allowed a detailed investigation of highly excited vibrational states of small polyatomic molecules. As excitation energy increases, molecular motion becomes chaotic and nonlinear techniques can be applied to their analysis. The corresponding spectra get also complicated, but some interesting low resolution features can be understood simply in terms of classical periodic motions. In this chapter we describe some techniques to systematically construct quantum wave functions localized on specific periodic orbits, and analyze their main characteristics. 

The metaiioporphyrins form a diverse class of molecules exhibiting complex and varied photochemistries. Until recently time-resolved absorption and fluorescence spectroscopies were the only methods used to study metailoporphyrln excited state relaxation in a submicrosecond regime. In this paper we present the first picosecond time-resolved resonance Raman spectra of excited state metaiioporphyrins outside of a protein matrix. The inherent molecular specificity of resonance Raman scattering provides for a direct probe of bond strengths, geometries, and ligation states of photoexcited metaiioporphyrins. 

We have also learned that VMP is an effective tool in molecular spectroscopy and molecular dynamics studies. It is effective, in particular, for determination of IVR lifetimes and for studying the vibrational spectroscopy of states that are difficult to study applying other methods. The above-mentioned limit of the size of the molecule is irrelevant here. For observing the mode selectivity in VMP, the vibrational excitation has to survive IVR in order to retain the selectivity since the subsequent electronic excitation has to be from the excited vibrational state. In contrast, monitoring vibrational molecular dynamics relies only on the efficacy of the excitation of the specific rovibrational state. When IVR is fast and rovibrational distribution reaches equilibrium, the subsequent electronic excitation will still reflect the efficacy of the initial rovibrational excitation. In other words, whereas fast IVR precludes mode selectivity, it facilitates the unraveling of the vibrational molecular dynamics. 

---