The verification of delta SCF and Slater's transition state theory for the calculation of core ionization energy.

The core ionization energies of second- and third-period elements of the molecules C2 H5 NO2 , SiF4 , Si(CH3 )4 , PF3 , POF3 , PSF3 , CS2 , OCS, SO2 , SO2 F2 , CH3 Cl, CFCl3 , SF5 Cl, and Cl3 PS are calculated by using Hartree-Fock (HF), and Kohn-Sham (KS) with BH&HLYP, B3LYP, and LC-BOP functionals. We used ΔSCF, Slater's transition state (STS), and two previously proposed shifted STS (1) and shifted STS (2) methods, which have been developed. The errors of ΔSCF and STS come mainly from the self-interaction errors (SIE) and can be corrected with a shifting scheme. In this study, we used the shifting parameters determined for each atom. The shifted STS (1) reproduces ΔSCF almost perfectly with mean absolute deviations (MAD) of 0.02 eV. While ΔSCF and STS vary significantly depending on the functional used, the variation of shifted STS (2) is small, and all shifted STS (2) values are close to the observed ones. The deviations of the shifted STS (2) from the experiment are 0.24 eV (BH&HLYP), 0.19 eV (B3LYP), and 0.23 eV (LC-BOP). These results further support the use of shifted STS methods for predicting the core ionization energies.

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table.

A comprehensive theoretical treatment is presented for the electronic excitation spectra of ca. 50 different mono-, di-, and tetrasubstituted naphthalenediimides (NDI) using time-dependent density functional theory (TDDFT) at ZORA-CAM-B3LYP/TZ2P//ZORA-BP86/TZ2P with COSMO for simulating the effect of dichloromethane (DCM) solution. The substituents -XHn are from groups 14-17 and rows 2-5 of the periodic table. The lowest dipole-allowed singlet excitation (S0 -S1 ) of the monosubstituted NDIs can be tuned from 3.39 eV for -F to 2.42 eV for -TeH, while the S0 -S2 transition is less sensitive to substitution with energies ranging between 3.67 eV for -CH3 and 3.44 eV for -SbH2 . In the case of NDIs with group-15 and -16 substituents, the optical transitions strongly depend on the extent to which -XHn is planar or pyramidal as well as on the possible formation of intramolecular hydrogen bonds. The accumulative effect of double and quadruple substitution leads in general to increasing bathochromic shifts, but the increased steric hindrance in tetrasubstituted NDIs can lead to deformations that diminish the effectiveness of the substituents. Detailed analyses of the Kohn-Sham orbital electronic structure in monosubstituted NDIs reveal the mesomeric destabilization of the HOMO as the primary cause of the bathochromic shift of the S0-S1 transition.

Vertical ionization potential benchmarks from Koopmans prediction of Kohn-Sham theory with long-range corrected (LC) functional.

The Kohn-Sham density functional theory (KS-DFT) with the long-range corrected (LC) functional is applied to the benchmark dataset of 401 valence ionization potentials (IPs) of 63 small molecules of Chong, Gritsenko and Baerends (the CGB set). The vertical IP of the CGB set are estimated as negative orbital energies within the context of the Koopmans' prediction using the LCgau-core range-separation scheme in combination with PW86-PW91 exchange-correlation functional. The range separation parameterµof the functional is tuned to minimize the error of the negative HOMO orbital energy from experimental IP. The results are compared with literature data, includingab initioIP variant of the equation-of-motion coupled cluster theory with singles and doubles (IP-EOM-CCSD), the negative orbital energies calculated by KS-DFT with the statistical averaging of orbital potential, and those with the QTP family of functionals. The optimally tuned LC functional performs better than other functionals for the estimation of valence level IP. The mean absolute deviations (MAD) from experiment and from IP-EOM-CCSD are 0.31 eV (1.77%) and 0.25 eV (1.46%), respectively. LCgau-core performs quite well even with fixedµ(not system-dependent). Aµvalue around 0.36 bohr-1gives MAD of 0.40 eV (2.42%) and 0.33 eV (1.96%) relative to experiment and IP-EOM-CCSD, respectively. The LCgau-core-PW86-PW91 functional is an efficient alternative to IP-EOM-CCSD and it is reasonably accurate for outer valence orbitals. We have also examined its application to core ionization energies of C(1s), N(1s), O(1s) and F(1s). The C(1s) core ionization energies are reproduced reasonably [MAD of 46 cases is 0.76 eV (0.26%)] but N(1s), O(1s) and F(1s) core ionization energies are predicted less accurately.

Theoretical design of triphenylamine-based derivatives with asymmetric D-D-π-A configuration for dye-sensitized solar cells.

The use of theoretical techniques in the structural development of dye-sensitized solar cells helps in the efficient screening of the dyes. To properly rationalize the dye's design process, benchmark calculations were conducted using long-range corrected exchange-correlation (xc) functionals with varying separation parameters to be able to predict the excited-state energies of triphenylamine-based dyes, namely: PPS, PSP, and PSS, wherein they differ at the π-conjugated bridge using thiophene and/or phenyl moieties. The results show that LC-ωPBE xc functional with an optimized parameter provided better correlation with the experimental results compared to the other functionals. The relative shifts of the absorption spectra, light harvesting efficiency, normal dipole moments, as well as the ionization potentials and electron affinities of the dyes were well-correlated with the experimental data. A new set of dyes was designed in an effort to increase its solar cell efficiency that was patterned after PSS with an additional donor moiety such as fluorene, cyclopentaindole, and pyrene attached asymmetrically at the triphenylamine ring. Among the newly designed dyes, analogs that contain 4-phenyl-1,2,3,4-tetrahydrocyclopenta[b]indole (I) and pyrido[2,3,4-5-imn]phenanthridine-5,10(4H,9H)-dione (P2) as the additional donor moiety produced the best photophysical properties and charge-transfer characteristics for a promising dye for solar cell applications.

Understanding the Density Functional Dependence of DFT-Calculated Electronic Couplings in Organic Semiconductors.

We present an analysis of the magnitude of density functional theory (DFT)-calculated intermolecular electronic couplings (transfer integrals) in organic semiconductors to give insight into the impact that the choice of functional has on the value of this parameter, which is particularly important in the context of charge transport. The major factor determining the magnitude of the calculated transfer integrals is the amount of nonlocal Hartree-Fock (HF) exchange within a given functional, with the transfer integrals increasing by up to a factor of 2 when going from 0 to 100% HF exchange for a series of conventional functionals. We underline that these variations in the transfer integrals are in fact to be expected, with the computed transfer integrals evolving linearly with the amount of HF exchange. We also use a long-range corrected functional to tune the contributions of (semi)local and nonlocal HF exchanges and highlight their respective roles as a function of intermolecular separation.