Excited states, calculation

Most of the semiempirical methods are not designed to correctly predict the electronic excited state. Although excited-state calculations are possible, particularly using a CIS formulation, the energetics are not very accurate. However, the HOMO-LUMO gap is reasonably reproduced by some of the methods. 

The HyperChem program from Hypercube Inc. and UniChem from Oxford Molecular can be used as graphic interfaces to Q-Chem. At the time we conducted our tests, it was not yet available on all the platforms listed as being supported. The current version is well designed for ground- and excited-state calculations on small or large organic molecules. 

Q-Chem also has a number of methods for electronic excited-state calculations, such as CIS, RPA, XCIS, and CIS(D). It also includes attachment-detachment analysis of excited-state wave functions. The program was robust for both single point and geometry optimized excited-state calculations that we tried. 

The following Gaussian keywords and options are useful for excited state calculations ... 

Note that we have included diffuse functions in the basis set. Diffuse functions are essential to obtaining good results for excited state calculations. 

This example once again illustrates the fact that Cl-Singles excited state calculations can find states which are detectable only by some mechanism other than optical spectroscopy. ... 

Finally, run another CASSCF 6,5)/6-31G(d) job to predict the energy of the ground state, using the same strategy as for the excited state. Retrieve the initial guess from the checkpoint file from the excited state calculation. 

Some n-electron charge density differences between the ground and first excited states calculated by the PPP-MO method for 4-aminoazobenzene,... 

Interestingly, after reaching the maximum at the 6-membered cycle, the yields drop again. This decrease in efficiency occurs despite the appreciable reduction in the distance between the terminal acetylenic carbons relative to the 6-membered analogue. Here, the efficiency may simply be a function of how photochemical excitation is distributed in the reactive excited state. Calculated enediyne geometries suggest the cyclization is more efficient for those enediynes where the terminal phenyl groups are rotated outside of the enediyne plane (Table 3). 

To perform excited-state calculations, one has to approximate the exchange-correlation potential. Local self-interaction-free approximate exchange-correlation potentials have been proposed for this purpose [73]. We can try to construct these functionals as orbital-dependent functionals. There are different exchange-correlation functionals for the different excited states, and we suppose that the difference between the excited-state functionals can be adequately modeled through the occupation numbers (i.e., the electron configuration). Both the OPM and the KLI methods have been generalized for degenerate excited states [37,40]. 

For excited state calculations, significant progress has been made based on the GW method first introduced by Hybertsen and Louie. [29] By considering quasi-partide and local field effects, this scheme has allowed accurate calculations of band gaps, which are usually underestimated when using the LDA. This GW approach has been applied to a variety of crystals, and it yields optical spectra in good agreement with experiment. 

In consequence, the most expensive steps of the ground- and excited-state calculations using methods based on the MMCC(2,3) approximation are essentially identical to the n nf noniterative steps of the ground-state CCSD(T) calculations uo and are the numbers of occupied and unoccupied correlated orbitals, respectively). Similar remarks apply to the memory and disk-space requirements. Clearly, these are great simplifications in the computer effort, compared to the higher-level EOMCC approaches, such as EOMCCSDT [43,44,55,56], particularly if we realize that we only have to use the Ti and T2 clusters, obtained in the CCSD calculations, to construct matrix elements of that enter 9Jt (2), Eqs. (58) and (59). In... 

Methods for generating excited-state wave functions and/or energies may be conveniently divided into methods typically limited to excited states that are well described as involving a single excitation, and other more general approaches, some of which carry a dose of empiricism. The next three sections examine these various methods separately. Subsequendy, the remainder of the chapter focuses on additional spectroscopic aspects of excited-state calculations in both the gas and condensed phases. 

Table 9.4 Solvent dependent driving forces for charge separation (CS) out of the porphyrin singlet excited state and charge recombination (CR) to the ground state/porphyrin triplet excited state calculated after the dielectric continuum model (dielectric constant e toluene 2.4 THF 7.6 oDCB 9.8, benzonitrile 24.9). The case, where charge recombination to the porphyrin triplet state is prohibited, is assigned as n.p. ...

R. Improta, V. Barone, G. Scalmani, M.J. Frisch, A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution. J. Chem. Phys. 125, 054103 (2006)... 

The 1 isomer is difficult to detect and identify by IR spectroscopy, since the IR spectrum only contains one weak line. In contrast, there are two transitions of intermediate strength in the Raman spectrum, and consequently Raman spectroscopy can be used for identification without the need of isotopic labeling. An alternative approach for detection is LIF spectroscopy. Excited state calculations, using linear and quadratic CCSD theory, indicates that the... 

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