D-aug-cc-pVDZ

Table 2.9 DFT/B3LYP/d-aug-cc-pVDZ and experimental results (atomic units) for the CME of pure liquid furan, thiophene and selenophene. A =632.8 nm, T=293.l5 K. Experimental geometries...

In two recent publications we have tried to characterize the excited state properties of 1 and 3 in order to facilitate their detection by LIF-spectroscopy. Our main tool in this effort has been equation of motion coupled cluster theory (EOM-CC). The EOM-CCSD method, which is equivalent to linear response CCSD, has been shown to provide an accurate description of both valence and excited states even in systems where electron correlation effects play an important role [39]. Computed transition energies for excitations that are of mainly single substitution character are generally accurate to within 0.1 eV. We have found the EOM-CCSD method to perform particularly well in combination with the doubly-augmented cc-pVDZ (d-aug-cc-pVDZ) basis set. This basis seems to provide equally balanced descriptions of ground and excited states,... 

EOM-CCSD/d-aug-cc-pVDZ vertical excitation energies (A Vexc) (in eV) and one photon oscillator strengths (/), and QR-CCSD/d-aug-cc-pVDZ two-photon transition probabilities (TPA) (in au) for (1). ... 

Kowalczyk et al. [121] have investigated the basis set dependence of calculated ORs at four different wavelengths, and of the lowest six states in the ECD spectrum, for (S)-2-chloropropionitrile optimized at the B3LYP/6-311++G(d,p) level of theory. The ORD was calculated at 633, 589, 436, and 355 nm. Six basis sets were selected to calculate the specific rotation with an origin-invariant GIAO approach aug-cc-pVDZ, aug-cc-pVTZ, aug-cc-pVQZ, d-aug-cc-pVDZ, d-aug-cc-pVTZ, and Sadlej-pVDZ (155, 326, 588, 207, 426, and 174 basis functions, respectively). All TDDFT calculations used the B3LYP functional. No solvation models were employed in the calculations. Experimental gas phase measurement... 

Fig. 8 The effect of basis set on the specific rotation of (S)-methyloxirane calculated with the B3LYP functional at 589 nm. The key labels the method of geometry optimization. Basis set numbers correspond to the following 1 = 6-31G(d), 2 = 6-31+-l-G(d,p), 3 = 6-31++G(2d,2p), 4 = cc-pVDZ, 5 = cc-pVTZ, 6 = aug-cc-pVDZ, 7 = d-aug-cc-pVDZ, 8 = mixed-cc-PVTZ (aug-cc-pVTZ(C,0) and aug-cc-pVDZ(H)), 9 = aug-cc-pVTZ, 10 = Sadlej-pVTZ. Data to prepare the plot were taken from [145]...

Table 17. Convergence of the anisotropy of the static hypermagnetizability An(0) of neon with the correlation treatment (from [39] finite field orbital-relaxed results (unless specified) for d-aug-cc-pVDZ, frozen core approximation for Is shell, numbers in atomic units.)...

Complete geometry optimization of structures 1-lV (Fig. 3) were conducted with several computational protocols including B2PLYP-D/aug-cc-pVDZ, B2PLYP-D/... 

Geometry optimization and frequency calculation at B2PLYP-D/ aug-cc-pVDZ... 

Figure 10 Contour plots of the lone-pair MO (a) and 3s Rydberg MO (b) for acetone in the O—CCC plane. Because of the too high potential for the virtual orbitals in ground-state HF treatments, the calculations refer to a ROHF/d-aug-cc-pVDZ treatment for the B2 cation ground state.

MRCI computations (d-aug-cc-pVDZ AO basis, B3LYP/TZV(d,p) ground-state geometry) are compared with experimental data in Table 5. A graphical comparison with an experimental gas-phase absorption spectrum is shown in Figure 12. 

Li et alP reported a theoretical study of the structure and interaction-induced dipole moment, mean polarizability and mean first hyperpolarizability of the NH3-HCl-(H20)n (n = 0 ) clusters. They relied on B3LYP calculations with large standard basis sets aug-cc-pVDZ, aug-cc-pVDZ-fBF (aug-cc-pVDZ augmented with suitable placed bond functions), aug-cc-pVTZ, d-aug-cc-pVDZ and t-aug-cc-pVDZ. The authors have reached important conclusion on the magnitude of electric properties. For the non-hydrated complex NH3-HCI the first hyperpolarizability, calculated with the d-aug-cc-pVDZ basis, is jS = — 3.35 e ao Eh while the respective result for NH3-HCI-H2O is 413.52 and increases to 886.41 for NH3-HC1-(H20)4. 

Excitation energies were calculated with the equation of motion coupled cluster theory with single and double excitations (EOM-CCSD) [87] and the Dunning s correlation-consistent d-aug-cc-pVDZ and aug-cc-pVTZ basis-sets [88]. 

Fig. 7.3 Dependence of the excitation spectra of water on the size of the quantum system n for calculations with the BLYP-D3 functional and the d-aug-cc-pVDZ basis-set...

The spectmm of liquid HCN is characterized by the presence of two allowed bands centered at 9.4 and 10.4 eV. A weakly allowed band on the red edge of the first allowed one (see inset panel) is also observed. Further details on the nature of the excitations defining each band can be found in Ref. [34]. Here, we will focus on some specific aspects that stress the importance of the presently adopted approach. By coupling a MBE decomposition scheme to BOMD configurations the electronic spectra can be calculated at the EOM-CCSD/d-aug-cc-pVDZ level for systems with a significant number of fragments n = 64 HCN monomers). The results based on the embedded supercell supermolecular systems show no significant dependence on the number n of HCN monomers included in the quantum system and supports the adequacy of the present approach when the number of monomers in the BOMD is relatively small. 

Fig. 4.1. The five lowest totally symmetric E+ energies (in Eh) of the BH molecule calculated in the d-aug-cc-pVDZ basis at the molecular ground-state equilibrium bond distance of 2.3289oo-...

Hartree-Fock interaction is attractive at the experimental minimum. The origin of this interaction is BSSE, whose spurious stabilization of the neon dimer outweighs the Pauli repulsion for small basis sets. These effects are illustrated on the left in Figure 8.24, where we have plotted the (uncorrected) Hartree-Fock potential-energy curve for various doubly augmented basis sets. As the cardinal number increases, the spurious Hartree-Fock minimum becomes shallower and located further out. We note that the potential-energy curve may contain several such spurious minima. Thus, the d-aug-cc-pVDZ curve has a minimum of —73 pEh at a separation of 6.1oo a shallower minimum of —14 pEh at a separation of 8.5ao-... 

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