An ab initio study of CX₃‐substitution (X = H, F, Cl, Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene

Abstract

We report a systematic ab initio and density functional theory (DFT) study of the electric properties of the X3CC≡CC≡CH (X = H, F, Cl, Br, and I) sequence of substituted diacetylenes. We rely on finite‐field Møller–Plesset perturbation theory and coupled‐cluster calculations with large, flexible basis sets. Our best values at the second‐order Møller–Plesset perturbation theory level for the mean dipole polarizability and second hyperpolarizability are $\overline {{\alpha} } $/e2aE = 64.46 (CH3), 65.59 (CF3), 110.11 (CCl3), 138.90 (CBr3), 184.98 (CI3) and $\overline {{\gamma} } $/e4aE = 21020 (CH3), 13469 (CF3), 32708 (CCl3), 57599 (CBr3), and 105251 (CI3). For comparison, the analogous MP2 values for diacetylene [P.Karamanis and G.Maroulis, Chem. Phys. Lett. 2003, 376, 403.] are $\overline {{\alpha} } $/e2aE = 49.17, and $\overline {{\gamma} } $/e4aE = 16227. For the mean first hyperpolarizability we report $\overline {{\beta} } $/e3aE = −205.8 (CH3), −55.7 (CF3), 120.8 (CCl3), 443.8 (CBr3), and 725.4 (CI3). Copyright © 2010 John Wiley & Sons, Ltd.

Applying Conventional Ab Initio and Density Functional Theory Approaches to Electric Property Calculations. Quantitative Aspects and Perspectives

“…We show that it is probably a distinct advantage to talk about the quality or predictive capability of a set of DFT methods instead of trying to obtain a picture of the potential of a single one. This strongly corroborates our recent strategy to rely on a given set of DFT methods in order to form a clear idea about the DFT perspective in electric property calculations [115,128,129]. …”

“…The ab initio methods are SCF, MP2, MP3, DQ-MP4, SDQ-MP4, MP4, CCSD, and CCSD(T). The choice of DFT methods leans heavily on previous experience [111][112][113][114][115]: B3LYP, B3PW91, PBEPBE, PBEPW91, mPW1PW91, and mPW1PBE as implemented in the GAUSSIAN suite of codes.…”

Theoretical investigation of the static (hyper)polarizabilities and reorganization energy of 4,5-dicyanoimidazole chromophore and derivatives containing benzene rings and a saturated bridge

“…For instance, in 6-31+G(d,p) basis set, the d gaussian-type functions (GTF) on C and the p-GTF on H have rather tight exponents. These exponents may not be in the optimal range for polarizabilities [31,32]. On the other hand, previous papers established that the second hyperpolarizability of organic molecules can be reasonably well calculated at MP2/6-31+G(d,p) level [14,15].…”

Nonlinear optical properties of rhenium(I) complexes: Influence of the extended π-conjugated connectors and proton abstraction

“…M a n u s c r i p t 4 analytical third energy derivatives, which are more efficient and less expensive [35,36]. For dipolar molecules, the first hyperpolarizability is generally related to the β vec value, which is the vector component of β along the dipole moment direction and given by the following:…”