Sadlej basis set

The ability of Sadlej basis sets [37] to provide reliable values of has been tested in a limited number of cases with encouraging results [11]. In the present work on benzene the Sadlej basis set yields theoretical estimates close to those obtained by Perrin et al. [16] and Kama et al. [17], but smaller than those reported by Augspurger and Dykstra [18]. The C-C bond distance retained in [18], however, is 1.397 A, compared to 1.395 Aused by us, see Refs. [38] and [40]. 

The first hyperpolarizability of p-enamino ketones as well as of its p-methoxy and p-cyano derivatives has been calculated ab initio (HF and MP2 levels with the Sadlej basis set) as well as using the AMI Hamiltonian with the aim of showing that p-enamino ketones could constitute a new class of second-order NLO compounds. It was shown that the substitution by a donor enhances the first hyperpolarizability whereas substitution by an acceptor is slightly detrimental. Moreover, electron correlation effects are large and lead to an increase of p by 250 to 400%. 

Five large basis sets have been employed in the present study of benzene basis set 1, which has been taken from Sadlej s tables [37], is a ( ()s6pAdl6sAp) contracted to 5s >p2dl >s2p and contains 210 CGTOs. It has been previously adopted by us in a near Hartree-Fock calculation of electric dipole polarizability of benzene molecule [38]. According to our experience, Sadlej s basis sets [37] provide accurate estimates of first-, second-, and third-order electric properties of large molecules [39]. 

In any event, we are confident that the computational approach developed in this study, owing to its efficient use of molecular symmetry, can help develop large basis sets for first and second hyperpolarizabilities. An important aim would be that of estimating, at least at empirical level, Hartree-Fock limits for these quantities. To this end the use of basis sets polarized two times, according to the recipe developed by Sadlej [37], would seem very promising. 

All calculations are scalar relativistic calculations using the Douglas-Kroll Hamiltonian except for the CC calculations for the neutral atoms Ag and Au, where QCISD(T) within the pseudopotential approach was used [99], CCSD(T) results for Ag and Au are from Sadlej and co-workers, and Cu and Cu from our own work, using an uncontracted (21sl9plld6f4g) basis set for Cu [6,102] and a full active orbital space. 

Kello, V. and Sadlej, A.J. (1996) Standardized basis sets for high-level-correlated relativistic calculations of atomic and molecular electric properties in the spin-averaged Douglas-Kroll (nopair) approximation 1. Groups Ib and 11b. Theoretica Chimica Acta, 94, 93-104. 

Dickson and Becke, 1996, use a basis set free numerical approach for obtaining their LDA dipole moments, which defines the complete basis set limit. In all other investigations basis sets of at least polarized triple-zeta quality were employed. Some of these basis sets have been designed explicitly for electric field response properties, albeit in the wave function domain. In this category belong the POL basis sets designed by Sadlej and used by many authors as well as basis sets augmented by field-induced polarization (FTP) func-... 

Sadlej, A.J. (1977) Molecular electric polarizabilities. Electric-field-variant (EFV) Gaussian basis set for polarizability calculations, Chem. Phys. Lett., 47,50-54. 

The dipole and quadrupole polarizability tensor components of LiH were calculated by MCSCF linear response theory with the basis set of Roos and Sadlej [57] which consists of 13s-, 8p-, 6d-, and 2f-type sets of uncontracted Gaussian functions on Li and 12s-, 8p-, and 5d-type sets of uncontracted Gaussians on H. Due to the small size of the molecule we could perform MCSCF calculations over the whole range of internuclear distances with a very large CAS 0000 520,10,10,4 p g present the tensor components, isotropic, and anisotropic values of the dipole polarizability tensor a as function... 

Many authors [8-10] have demonstrated that the CP method undercorrects the BSSE. Moreover, Karlstrom and Sadlej [11] pointed out that addition of the partner orbitals to the basis set of a molecule not only lowers its energy, in accordance with the variation principle, but also affects the monomer properties (multipole moments and polarizabilities). Latajka and Scheiner [12] found that in a model ion-neutral system such as Li" -OH2, this secondary BSSE can be comparable in magnitude to the primary effect at both SCF and MP2 levels. The same authors also underlined the strong anisotropy of secondary error [13]. 

An alternative experiment that measures the same vibrational fundamentals subject to different selection rules is Raman spectroscopy. Raman intensities, however, are more difficult to compute than IR intensities, as a mixed third derivative is required to approximate the change in the molecular polarizability with respect to the vibration that is measured by the experiment. The sensitivity of Raman intensities to basis set and correlation is even larger than it is for IR intensities. However, Halls, Velkovski, and Schlegel (2001) have reported good results from use of the large polarized valence-triple-f basis set of Sadlej (1992) and... 

Studies using the GGA- (BLYP) and hybrid- (HCTH, B3LYP, B97, B97-1) functionals combined with the Sadlej s basis set demonstrate that all considered functionals also lead to very reasonable dipole moments for a representative a set... 

Sadlej, A.J., Medium-size polarized basis-sets for high-level-correlated calculations of molecular electric properties. 4. Third row atoms - Ge through Br. Theor. Chim. Acta (1991) 81 45-63. 

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]...

Scott, A. R Radom, L. Harmonic vibrational frequencies an evaluation of Hartree-Fock, Moller-Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors, J. Phys. Chem. 1996,100, 16502-16513. Halls, M. D. VeUcovski, J. Schlegel, H. B. Harmonic frequency scaling factors for Hartree-Fock, S-VWN, B-LYP, B3-LYP, B3-PW91 and MP2 with the Sadlej pVTZ electric property basis set, Theor. Chem. Acc. 2001,105, 413-421. 

Cybulski et al. furnish an example of the sensitivity of the various perturbation components of the H-bond energy to the choice of basis set. In their study of the dimer of HF, 6-3IG refers to a standard split-valence set, with polarization functions. GD is similar in character but was designed to specifically address the dispersion energy more accurately. The S2 set was proposed by Sadlej to produce reliable dipole moments and polarizabilities of the monomers, augmented by extended polarization functions (/on F d on H). Well-... 

Karlstrom, G. and Sadlej, A. J., Basis set superposition effects on properties of interacting systems. Dipole moments and polarizabilities, Theor. Chim. Acta 61, 1-9 (1982). 

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