First-order Nonlinear Optical Response of C2Bn-2H n-1X (n = 14-17; X = H, Li, Na, K, F, Cl, Br) Carboranes: Insights from DFT and TD-DFT Calculations (original) (raw)
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Theoretical Chemistry Accounts, 2014
The nonlinear optical (NLO) properties of Nethyl dicyanocarbazole (1), N-ethyl cyanoethylacetatecarbazole (2), and N-ethyl dimethylacetatecarbazole (3) are studied with traditional hybrid and long-range corrected (LC) density functional theory (DFT) methods. The carbazoles are predicted to have planar structures with a high degree of p-conjugation and charge transfer, resulting in measurable NLO responses. The DFT data here calculated allow us to refine and correct previously reported experimental hyperpolarizabilities for these compounds. Experimental UV-vis absorption bands (related to hyperpolarizabilities estimated via solvatochromism) are also accurately reproduced by LC-DFT when using gap fitting schemes. The effects of different functionals on the HOMO-LUMO energy gaps and eventually on the total hyperpolarizabilities are discussed.
Linear and Nonlinear Optical Properties of Three-Coordinate Organoboron Compounds
Journal of Solid State Chemistry, 2000
Three-coordinate boron, isoelectronic with a trigonal planar carbonium ion, possesses a vacant p orbital which can conjugate with an organic system and thus serve as a acceptor. We and others have prepared a series of symmetric compounds of the general form (mes) 2 BEXNB(mes) 2 [mes ؍ mesityl ؍ 2,4,6 Me 3 C 6 H 2 ; EXN ؍ conjugated organic system such as +(p-C 6 H 4 ) n + or trans+trans+CH؍CH+(p-C 6 H 4 ) n +CH؍CH+] as well as donor+acceptor compounds of the general form DNXNB(mes) 2 [D ؍ donor such as MeO, MeS, H 2 N, Me 2 N, Ph 2 P, ferrocenyl; NXN ؍ conjugated organic system such as +C 6 H 4 +, +C 6 H 4 +CH؍CH+, +C 6 H 4 +CY Y C+, +C 6 H 4 +CH؍CH+ C 6 H +] and examined representative singlecrystal structures as well as linear (UV+vis absorption and 6uorescence) and second-and third-order nonlinear optical properties (by electric 5eld-induced second harmonic generation (EFISH) and third harmonic generation (THG)). The bulky mesityl groups protect the boron centers from hydrolysis. Many of the compounds are highly 6uorescent, with the unsymmetric ones displaying limited solvatochromic behavior in absorption spectra but signi5cant solvatochromic e4ects in their emission spectra consistent with small dipole moments in the ground state and large dipole moments in the excited states. Results from other groups on the use of related boron compounds as either electron-transport materials or emitting agents in electroluminescent devices, and on the preparation and optical properties of three-coordinate boron-containing conjugated polymers are presented. Preliminary results of extended HuK ckel (EH) and density functional (DF) molecular-orbital calculations on representative symmetric diboron compounds and extended HuK ckel tight-binding (EHTB) calculations on a model boron-containing polymer are reported. The B(mes) 2 group is a good acceptor, and three-coordinate boron moieties show signi5cant promise for use in molecular and polymeric optical materials.
Russian Journal of Physical Chemistry A, 2019
In this study, the substituent effect on the optical and electronic properties of 4-substituted ferrocenylethynylbenzenes was investigated by adopting the hybrid meta exchange-correlation functional of M06-2X. The frontier orbitals and the highest occupied molecular orbitals-lowest unoccupied molecular orbitals gaps of the substituted compounds were determined and the corresponding electronic transitions were unraveled using gas-phase time-dependent density functional theory calculations. Also, the nonlinear optical properties related to hyperpolarizability were discussed for both neutral and oxidized states of the molecules. Correlations between the evaluated properties and Brown's constant were explored.
Dalton Transactions, 2013
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Indian Journal of Chemistry -Section A
In this paper, the structural, electronic, non-linear optical (NLO) properties and vibrational frequencies of 4-(methoxycarbonyl)-phenylboronic acid have been examined theoretically using ab initio Hartree-Fock (HF) and Density Functional Theory (DFT/B3LYP) methods applying the standard 6-311++G(d,p) basis set. 1 Hand 13 C NMR chemical shifts are calculated by employing the direct implementation of the gauge including-atomic-orbital (GIAO) method at the B3LYP/6-311++G(d,p) and HF/6-31G(d) levels of the theory. There are two conformers, cis-trans(ct) and trans-cis (tc) for title molecule. The energy difference between ct and tc conformers of studied molecule are of 0.126 kcal/mol with B3LYP/6-311++G(d,p) and 0.138 kcal/mol with HF/6-311++G(d,p), respectively. The conformer ct is more stable than the conformer tc. Also, the energy gap differences between the highest occupied and the lowest unoccupied molecular orbitals, dipole moment, polarizability and first static hyperpolarizability are calculated as a function of both dihedral angle (C3-C4-C7-O3), between methoxycarbonyl group (CH 3-O-CO-) and benzene ring, and dihedral angle (C2-C1-B-O1), between boronic acid group (-B(OH) 2) and benzene ring. In the change of the energy gap and polarizability depending on dihedral angles, it is shown that the polarizabilities follow inverse relationship the energy gaps.
Ab initio study of nonlinear optical properties of aromatic fused rings
Chemical Physics Letters, 2013
ABSTRACT The nonlinear optical properties of benzene, naphthalene, anthracene, and pyrene are investigated. Static and dynamic polarizability, α(-ω; ω), and second hyperpolarizability, corresponding to dc electric-field-induced Kerr effect (DCKE), intensity dependent refractive index (IDRI), dc electric field-induced second harmonic generation (EFISHG), and third harmonic generation (THG) have been calculated. The calculated α and γ show good agreement with the available theoretical and gas-phase experimental data. The second hyperpolarizabilities exhibit the following trend: γ(THG) > γ(EFISHG) > γ(IDRI) ˜ γ(DCKE) > γ(static). We find that the second hyperpolarizabilities increase as the number of rings in the system increases in either dimension, but the magnitude of increase is more pronounced along the molecular chain axis.
Physical Chemistry Research, 2022
Density Functional Theory calculations, in the ground state of 2-Phenylbenzofuran, were carried out using the GGA-PBE, PBV86 and meta-GGA-TPSS hybrid functionals with 6-31G (d, p) as a basis set. First, theoretical calculations were performed using these functionals to obtain the stable conformer of the molecule. In addition, Mulliken population natural population and natural bond orbital analyses were calculated. The molecular electrostatic potential, band gap energies, global, local chemical reactivity descriptors and non-linear optical (NLO) properties were studied. Additionally, the NLO properties of 2-Phenylbenzofuran and those of its derivatives were investigated by GGA-PBE/6-31G (d,p) level of theory. The first-order hyperpolarizability value of all 2-Phenylbenzofuran derivatives was found within the range extending from 4.00 × 10-30 to 43.57 × 10-30 (esu). It indicated that they possess remarkable NLO properties. In addition, a multiple linear regression procedure was used t...
Chinese Science Bulletin, 2012
In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the secondorder nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C 6 H 5-C 2 B 10 H 10 (1), R=F(2), R=Me(3), R=NO 2 (4), R=NH 2 (5)). The static first hyperpolarizabilities ( tot) of the RTAB molecules can be switched by binding one F to the boron center (RTAB′) or one-electron reduction (RTAB"). The DFT-FF calculations show that the tot values of 2′, 3′ and 5′ decrease while those of 1′ and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the tot value of reduced form 1″ is 508.69×10 30 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E 0) and thus large tot values for the reduced forms.